KR20040086381A - Multifunctional monomers and their use in making cross-linked polymers and porous films - Google Patents

Abstract

The present invention comprises at least two dienophile groups and at least two ring structures, wherein the ring structure has two conjugated carbon-carbon double bonds and leaving groups L, and the ring structure is in the presence of heat or other energy sources. When reacted with the dienophile, the leaving group L is released to form an aromatic ring structure.

The present invention also relates to curable oligomers or polymers and higher crosslinked polymers made from such monomers. In addition, the present invention relates to a method of preparing a porous film by mixing such monomers or oligomers thereof with porogens, curing the polymer and removing the porogens.

Description

Multifunctional monomers and their use in making cross-linked polymers and porous films

Crosslinked or crosslinkable polyarylenes that are stable at high temperatures and have good electrical insulation properties are known to be useful in the manufacture of microelectronic devices. U.S. Patent No. 5,965,679 to Godschalx et al. Discloses a process for preparing such materials by reacting a multifunctional compound having at least two cyclopentadienone groups with a polyfunctional compound having at least two aromatic acetylene groups (multi-tubes). At least some of the functional compounds have three or more reactive groups). These materials are useful as interlayer dielectrics in the manufacture of integrated circuits and as dielectrics in the manufacture of other microelectronic devices. Godschalx et al. Also disclose monomers containing one cyclopentadienone group together with two aromatic acetylene groups and polymers prepared from these monomers. Typically these materials are spin applied onto a substrate followed by a hotplate baking step and then cured in an oven at about 400 ° C.

International Patent Publication No. WO 01/38417 discloses controlling the modulus of polymers as suggested by Guardwicks et al. By controlling the reactant proportion of guard fences or by adding other reactive materials to the product of monomers or partially polymerized guardtips. It is described that it may be desirable.

US Pat. No. 6,172,128 discloses aromatic polymers having cyclopentadienone groups capable of reacting with aromatic polymers containing phenylacetylene groups to provide branched or crosslinked polymers. US Pat. No. 6,156,812 discloses polymers containing both cyclopentadienone groups and phenyl acetylene groups in the polymer backbone.

Summary of the Invention

The inventors have discovered a new class of monomers and polymers made from these monomers having some or all of the following significant advantages. These monomers generally exhibit rapid and easily controlled reactivity, allowing partial polymerization or oligomerization, subsequent processing and ultimately curing or crosslinking of the composition. When these monomers are polymerized, the coefficient generally increases rapidly up to the plateau group value, indicating that the polymer can reach the gel point and / or vitrification point fairly quickly. These monomers are polymerized to produce aromatic polymers with high crosslink density. This polymer exhibits excellent thermal stability at high temperatures. Advantageously, these materials can be cured at temperatures in the range of about 200-300 ° C. past their gel points. Thus, a less intense heating step and / or a shorter time is required before solvent application of the additional layers onto the film. Moreover, the system does not require the use of comonomers, thereby reducing the risk of improper addition or inadequate proportion of reactants, simplifying the preparation of curable oligomers or polymers. Finally, in some preferred embodiments, partially polymerized materials have sufficient solubility so that a single solvent system can be used, which simplifies the manufacturing process and potentially prevents application problems that may occur when using mixed solvent systems.

Thus, according to the first aspect, the present invention comprises at least two dienophile groups and at least two ring structures, wherein the ring structure has two conjugated carbon-carbon double bonds and a leaving group L, and the ring structure is When reacted with the dienophile in the presence of heat or other energy source, the leaving group L is released to form an aromatic ring structure.

According to a second aspect, the invention is a branched curable oligomer or polymer made from such monomers. The present invention is also a branched curable oligomer or polymer containing reactive functional groups as side chain groups, terminal groups, and groups present in the main chain of the oligomer or polymer.

According to a third aspect, the present invention is a higher crosslinked polymer made from such monomers or made by curing a curable oligomer or polymer.

According to a fourth aspect, the invention is a composition comprising the branched curable oligomer and porogen of the second aspect. Porogen is herein a component that can be removed from a gelled polymer or more preferably a vitrified (ie, fully cured or crosslinked) by solvent or more preferably by thermal decomposition to form pores. . Other embodiments are methods of making porous films using these compositions and articles made by such methods.

According to a fifth aspect, the present invention provides the above-mentioned monomer, and partially polymerizes the monomer to contain the dienophile group and the ring structure as side chain groups, terminal groups, and oligomers or groups present in the main chain of the polymer. Or forming a polymer, and applying a composition comprising an oligomer or curable polymer onto a substrate and curing to form a crosslinked aromatic polymer.

According to a sixth aspect, the present invention is a product produced by the above method.

The present invention was completed with the support of the US Federal Government under cooperative arrangement number 70NANB8H4013 awarded by NIST. The federal government has certain rights in the invention.

The present invention relates to monomers having at least two different reactive functional groups and to aromatic polymers prepared from these monomers. More specifically, these polymers are useful as dielectric materials in the manufacture of microelectronic devices.

Monomer And their synthesis

The monomer of the present invention preferably contains 2 to 4, more preferably 2 or 3, most preferably 2 ring structures having two conjugated carbon-carbon double bonds and leaving group L. Examples of suitable ring structures include cyclopentadienone, pyrone, furan, thiophene and pyridazine. The monomers of the present invention preferably comprise 2, 3, 4, 5, 6, 7, 8, 9 or 10 dienophile groups. Examples of suitable dienophile groups are acetylene groups, preferably phenyl acetylene groups, nitrile groups and the like.

Preferably the ring structure is a five-membered ring where L is -O-, -S-,-(CO)-or-(S0 ₂ )-or a six-membered ring where L is -N = N- or -O (CO)-. Optionally, two carbon atoms of the ring structure and their substituent groups may together form an aromatic ring, ie a five or six membered ring structure may be fused to form an aromatic ring. Most preferably, L is-(CO)-such that it is a valence cyclopentadienone group.

The monomers preferably have two or three ring structures. Preferred monomers having two ring structures are typically represented by the formula Z-X-Z.

In the above formula, Z is

{Where L is -O-, -S-, -N = N-,-(CO)-,-(S0 ₂ )-or -O (CO)-, and Y is each independently hydrogen, unsubstituted or An inertly substituted aromatic group, an unsubstituted or inertly substituted alkyl group or -WC≡CV, wherein W is an unsubstituted or inertly substituted aromatic group, and V is hydrogen, unsubstituted or inactive Substituted aromatic group, or an unsubstituted or inertly substituted alkyl group).

X is an unsubstituted or inertly substituted aromatic group or -W-C≡C-W-, wherein W is as defined above, provided that at least two X and Y groups comprise an acetylene group.

Inertly substituted group herein means a substituent group that does not interfere with the polymerization reaction of the monomer.

Preferred monomers having three ring structures are represented by the formula Z-X-Z'-X-Z, wherein Z '

And L, Y, Z and X are as defined above).

One class of preferred monomers is represented by formula (I).

In formula (I) above, X and Y are as defined above. Preferably, 2, 4 or 6 Y groups comprise acetylene groups.

Non-limiting examples of unsubstituted or inertly substituted divalent aromatic moieties include

Wherein Q is -O-, -S-, alkylene, -CF _2- , -CH ₂ -and the following inactive groups

(Wherein Ph is a phenyl group). Likewise, unsubstituted or inertly substituted monovalent aromatic moieties include those in which one of the bonds shown in the moiety is linked to hydrogen, an alkyl group having 1 to 10 carbon atoms, and the like. Unsubstituted or inertly substituted alkyl moieties may include, but are not limited to, alkyl having 1 to 20, preferably 1 to 10 carbon atoms.

Specific preferred monomers include the following.

Mixture of

Mixture of

Mixture of

Mixture of

Monomers of the invention having a ring structure of cyclopentadienone can be prepared, for example, by condensing (or similar reactions) of substituted or unsubstituted benzyl ketones using conventional methods, for example. Kumar et al., Macromolecules, 1995, 28, 124-130; Ogliaruso et al., J. Org. Chem., 1965, 30, 3354; Ogliaruso et al., J. Org. Chem., 1963, 28, 2725; Wiesler et al., Macromolecules, 2001, 34, 187; Baker et al., Macromolecules, 1979, 12, 369; Tong et al., J. Am. Chem. Soc. 1997, 119, 7291; And US Pat. No. 4,400,540, all of which are incorporated herein by reference]. Monomers with other structures can be prepared as follows: Pyron can be prepared using conventional methods described in the following references and references cited therein. Braham et al., Macromolecules 11 , 343 (1978). ; Liu et al., J. Org. Chem. 61 , 6693-99 (1996); van Kerckhoven et al., Macromolecules 5 , 541 (1972); Schilling et al., Macromolecules 2 , 85 (1969); Puetter et al., J. Prakt. Chem. 149 , 183 (1951). Furans can be prepared using conventional methods described in the following references and references cited therein. Feldman et al., Tetrahedron Lett. 47, 7101 (1992); McDonald et al., J. Chem. Soc. Perkin Trans. 1 1893 (1979). Pyrazines can be prepared using conventional methods described in the following references and references cited therein (Turchi et al., Tetrahedron 1809 (1998)). All cited references listed above are incorporated herein by reference.

For example, the following reaction is an example of a synthesis method that can be used to prepare the preferred monomers of Formulas II-V.

Wherein R and R ₁ are hydrogen or phenylethynyl group.

Synthetic monomers

And

to be.

When DPA-1 reacts with TK-2, a monomer of Formula II is formed. When DPA-2 reacts with TK-1, a monomer of Formula III is formed. When DPA-3 reacts with TK-1, a monomer of Formula IV is produced. When DPA-3 reacts with TK-2, a monomer of Formula V is produced. When DPA-1 reacts with TK-4, a monomer of formula VI is produced. When DPA-2 reacts with TK-2, a mixture of three compounds is formed, which are stereoisomers, all having two cyclopentadienone groups and four acetylene groups (Formula XX). Reaction of DPA-2 with TK-3 results in the formation of a mixture of monomers having three cyclopentadienone groups and three acetylene groups (Formula XXI). Reaction of DPA-2 with TK-4 results in the formation of a mixture of monomers having three cyclopentadienone groups and five acetylene groups (formula XXII). Reaction of DPA-3 with TK-3 results in the formation of monomers having three cyclopentadienone groups and six acetylene groups (formula XXIII). Reaction of DPA-3 with TK-4 results in the formation of monomers having three cyclopentadienone groups and eight acetylene groups (Formula XXIV).

As a further example, DPA-1 and TK-1 are known compounds and DPA-2, DPA-3 and TK-2 can be synthesized by the examples described below. TK-3 can be synthesized as follows:

TK-4 can also be synthesized as follows:

More specifically, monomers of formula (II) may be conveniently prepared using the methods described in Examples 1 or 13 herein. Briefly, the process comprises (a) chlorination of 4-bromophenylacetic acid with thionyl chloride to produce 4-bromophenylacetyl chloride, (b) aluminum chloride, and a solvent that is essentially inert to both the reactants and the product. Phenyl ether diacylated with 4-bromophenylacetyl chloride with (c) dimethylsulfoxide and hydrobromic acid to improve the diacylated product with Konblum (D) bis (phenylethynylated) the bis (4-bromophenyl) tetraketone product with phenylacetylene using (d) a palladium catalyst, a tertiary amine, and a solvent essentially inert to both the reactants and the product; (e) bis (phenylethynyl) tetraketone and 1,3-diphenylacene using quaternary ammonium hydroxide catalysts and one or more solvents that are essentially inert to both reactants and products Through a double-aldol reactions and forming a bis (cyclopentadienyl rice). The purity of the monomers can vary widely depending on the reaction conditions used to form the final synthesis step (e) bis (cyclopentadienone). As such, the reactants and reaction conditions used in Example 1 E provide a product containing approximately 75 area% of monomer II according to HPLC analysis. The reactants and reaction conditions in Example 13 D are adjusted to provide high purity AABB monomers containing greater than 98.5 area% monomer II according to HPLC analysis. High purity monomers II are generally most preferred for the uses presented herein.

Monomers of formula (VIII) may also be conveniently prepared using the methods described in Examples 1 or 13 herein. The process consists essentially of the process used for the preparation of the monomers of formula (II), but 3-bromophenylacetyl chloride is used instead of 4-bromophenylacetyl chloride. Specific synthesis of monomers of formula (VII) is described in Example 18 of the present invention.

Similarly, monomers of formula (XII) may be conveniently prepared using the methods described in Examples 1 or 13 herein. The process consists essentially of the process used for the preparation of the monomers of formula (II), but 3,5-dibromophenylacetyl chloride is used instead of 4-bromophenylacetyl chloride. It is also understood that (d) bis (phenylethynylation) becomes tetrakis (phenylethynylation) because there are more two stoichiometric aryl bromide groups in the tetraketone precursor.

Non-ether bound monomers of formula (VIII) may be conveniently prepared using the methods described in Example 5 herein. Briefly, the process comprises (a) chlorination of potassium 1,3-phenylenediacetate with thionyl chloride to produce 1,3-phenylenediacetyl chloride, and (b) aluminum chloride, and essentially both the reactants and the product. Bromobenzene is fritted-crafts acylated with 1,3-phenylenediacetyl chloride using an inert solvent, (c) dimethylsulfoxide and hydrobromic acid are used to improve the conbulg oxidation of the acylation product, (d) Bis (4-bromophenyl) tetraketone product is bis (phenylethynylated) with phenylacetylene using a palladium catalyst, a tertiary amine, and a solvent that is essentially inert to both reactants and products, and (e ) Double aldol reaction of bis (phenylethynyl) tetraketone and 1,3-diphenylacetone using quaternary ammonium hydroxide catalyst and at least one solvent that is essentially inert to both reactants and products Through and forming a bis (cyclopentadienyl rice).

Non-ether bound monomers of formula (VIII) may be conveniently prepared using the methods described in Example 5 herein. The process consists essentially of the process used for the preparation of the monomers of formula (VII), but 1,4-phenylenediacetyl chloride is used instead of 1,3-phenylenediacetyl chloride.

Non-ether bound monomers of formulas XIII and XIV can likewise be conveniently prepared using the methods described in Example 5 herein. The process consists essentially of the process used for the preparation of the monomers of formula (VII), but (b) 1,3-dibro instead of bromobenzene in acylation with 1,3- or 1,4-phenylenediacetyl chloride. Parentbenzene is used. It is also understood that (d) bis (phenylethynylation) becomes tetrakis (phenylethynylation) because there are more two stoichiometric aryl bromide groups in the tetraketone precursor.

Asymmetric monomers of Formulas (X) and (XI) may be conveniently prepared using the methods described previously herein. As a specific example, asymmetric monomers of Formula (XI) can be prepared by Friedel-Crafts monoacylation of phenyl ether with 3,5-dibromophenylacetyl chloride, the monoacylation product being a mixture of products, eg via silica gel chromatography. Recovered from The monoacylated product 4-[(3,5-dibromophenyl) acetyl] phenyl ether was then monoacylated with phenylacetyl chloride to give 4-[(3,5-dibromophenyl) acetyl ] -4 '-(phenylacetyl) phenyl ether is produced. In addition, it is also possible to produce a corresponding diketone by an improved cone oxidization of the 4-[(3,5-dibromophenyl) acetyl] phenyl ether monoacylation product prior to the second monoacylation. . Subsequently, as mentioned above, (c) dimethylsulfoxide and hydrobromic acid are used to improve the cone oxidization of the acylation product, and (d) are essentially inert to both the palladium catalyst, tertiary amine, and both reactants and products. A solvent is used to bis (phenylethynylate) the 3,5-dibromophenyl tetraketone product with phenylacetylene, and (e) at least one quaternary ammonium hydroxide catalyst and essentially inert to both the reactants and the product. A synthetic step of forming bis (cyclopentadienone) via a double aldol reaction of bis (phenylethynyl) tetraketone and 1,3-diphenylacetone using a solvent is performed to provide an asymmetric monomer of formula (XI).

Monomers of Formula (XV) may be conveniently prepared using the methods described previously herein. Specifically, Friedel-Crafts monoacylation of phenyl ether with 3,5-dibromophenylacetyl chloride is carried out, and the monoacylated product is recovered from the product mixture, for example via silica gel chromatography. The monoacylated product 4-[(3,5-dibromophenyl) acetyl] phenyl ether obtained was then monoacylated with 4-bromophenylacetyl chloride to give 4-[(3,5-dibro Mophenyl) acetyl] -4 '-[(4-bromophenyl) acetyl] phenyl ether. It is also possible to produce the corresponding diketone by improved convolution oxidation of the 4-[(3,5-dibromophenyl) acetyl] phenyl ether monoacylation product prior to the second monoacylation. Subsequently, as mentioned above, (c) dimethylsulfoxide and hydrobromic acid are used to improve the conbulg oxidation of the acylation products, and (d) are essentially inert to both palladium catalysts, tertiary amines, and both reactants and products. Three bromophenyl groups in the tetraketone product using a solvent, phenylethynylated with phenylacetylene, and (e) a quaternary ammonium hydroxide catalyst and one or more solvents that are essentially inert to both the reactants and the product. A synthetic step of forming bis (cyclopentadienone) via a double aldol reaction of tris (phenylethynyl) tetraketone and 1,3-diphenylacetone is performed to provide a monomer of formula XV.

Monomers of Formula (XXV) may be conveniently prepared using the methods described previously herein. Specifically, bromobenzene is fritted-crafts diacylated with 5-bromo-1,3-phenylenediacetyl chloride and then (c) diacylated products using dimethylsulfoxide and hydrobromic acid as mentioned above. And tris (phenylethynylated) the tribromo tetraketone product with phenylacetylene using an improved cone oxidized (d) palladium catalyst, tertiary amine, and a solvent essentially inert to both the reactants and the product. (e) bisdol through a double aldol reaction of tris (phenylethynyl) tetraketone and 1,3-diphenylacetone using quaternary ammonium hydroxide, catalyst and at least one solvent that is essentially inert to both reactants and products A synthesis step is carried out to form (cyclopentadiene).

Monomers of the general formula (XXVI) are selected from 4,4'-bis {[3,5-bis (phenylethynyl) phenyl] glyoxalyl} phenyl ether and 1,3-bis (4-phenylethynylphenyl-2-propanone It can be prepared via a double aldol condensation reaction.

Monomers of Formula (XXIII) are diacylated with (a) stoichiometric excess of diphenyl oxide with oxalyl chloride, (b) diacylated with 3,5-dibromophenylacetyl chloride, (c) oxidation, (d) Tetra (phenylethynylation), and (e) can be prepared by condensation.

Monomers of Formula (XXVII) may be prepared as described in Example 40.

Further examples of monomers of the invention, such as those represented by formulas XVI-XVIII, are prepared using the synthetic methods described herein and any other method known to those of ordinary skill in the art.

Once the monomers are synthesized, it is desirable to purify them. In particular, manufacturing methods for use as organic polymer dielectrics for electronic applications require the removal of metals and ionic materials. Preferably, these impurities can be removed by any known purification method including water washing and recrystallization.

Curable Oligomer And the formation of polymers

Without being bound by theory, polyphenylene oligomers and polymers are dienes and dienophiles (e.g., acetylene groups) containing ring structures (e.g., cyclopentadienone groups or pyron groups) when the mixture of monomers and suitable solvents are heated. It is believed to form through the Diels-Alder reaction. The reaction temperature and time required for the reaction will depend on the degree of polymerization desired. In addition, the higher the temperature, the shorter the reaction time required. Preferably, the B-step (or partial polymerization) reaction takes place for 1 to 72 hours at a temperature of 100 to 300 ° C. Carefully observe the B-step (or partial polymerization) reaction to avoid hasty gel formation. Depending on when the B-step reaction is terminated, there may be residual monomer remaining in the mixture after the B-step. Percentage of unreacted monomers can be determined by visual spectrum analysis or SEC analysis. The number average molecular weight of the material following the B-step is preferably in the range of 2,000 to 10,000.

Non-limiting examples of suitable solvents include mesitylene, methyl benzoate, ethyl benzoate, dibenzyl ether, diglyme, triglyme, diethylene glycol ether, diethylene glycol methyl ether, dipropylene glycol methyl ether, di Propylene glycol dimethyl ether, propylene glycol methyl ether, dipropylene glycol monomethyl ether acetate, propylene carbonate, diphenyl ether, cyclohexanone, butyrolactone and mixtures thereof. Preferred solvents are mesitylene, gamma-butyrolactone, cyclohexanone, diphenyl ether and mixtures of two or more of these solvents.

Separately, the monomers can be polymerized in one or more solvents at elevated temperatures, the resulting solution of oligomers can be cooled and then combined with one or more additional solvents to assist the process. Alternatively, the monomer can be polymerized at one or more solvents at elevated temperature to form oligomers, which can be isolated by precipitating it in a nonsolvent. Isolated oligomers can then be redissolved in a suitable solvent for the process.

Due to the unique structure of the monomers used, oligomers or polymers that have undergone B-staged or partially polymerized are highly branched and have reactive groups found in the main chain of the polymer as well as branched and terminal groups (ie, dienophiles, And a ring structure containing a conjugated carbon-carbon double bond and a leaving group, preferably an acetylene group and a cyclopentadienone group). The advantage of this is that it can provide a relatively high crosslink density.

The monomers of the present invention may also be used as comonomers with other monomers that may be copolymerized with these monomers, for example, via Diels-Alder reaction or acetylene acetylene reaction.

Curable Oligomer Preparation and Higher Order of Composition Crosslinked Formation of structures

Compositions with or without additives may be solvent applied, for example, by spin-application onto a suitable substrate. These oligomers, especially preferred oligomers derived from cyclopentadienone and aromatic acetylene functional monomers, are useful for the formation of films with very low dielectric constants in the manufacture of integrated circuit devices. Thus, these oligomers can of course also be used with other types of substrates, but it may be desirable to apply them onto substrates including transistors and / or metal interconnects.

When further heating the solution or the product to which the solution is applied, preferably to a temperature of 200 to 450 ° C., the remaining reactive ring groups (eg cyclopentadienone groups) and the remaining dienophile groups (eg acetylene groups) Diels-Alder reactions may cause further reactions (eg crosslinking or chain extension) to increase the molecular weight. Further crosslinking can also occur through reactions between dienophile groups, such as acetylene / acetylene reactions. The curing reaction can be carried out in a hotplate or oven baker, depending on the manufacturing plant design and efficiency.

Other components that may be added to the composition include fillers such as glass beads, glass fibers, hollow bodies, graphite fibers, carbon black, polymer powders; Adhesion promoters such as aromatic and aliphatic alkoxy, or acyloxy silanes including silanes having reactive vinyl groups, and porogens.

Porogens are components that can be removed from the gelled polymer, more preferably vitrified (ie, fully cured or crosslinked) by solvent or more preferably by thermal decomposition to form pores. Suitable porogens include polystyrenes such as polystyrene and poly-α-methylstyrene; Polyacrylonitrile, polyethylene oxide, polypropylene oxide, polyethylene, polyacetic acid, polysiloxane, polycaprolactone, polyurethane, polymethacrylate, polyacrylate, polybutadiene, polyisoprene, polyamide, polytetrahydrofuran, poly Vinyl chloride, polyacetals, amine-capped alkylene oxides, random or block copolymers of such polymers, and hydrogenated or partially hydrogenated modifications of such polymers. Porogens may actually be linear, branched, higher branched, twig or star structures. Porogens are preferably characterized in that they form discrete regions in the matrix material. Some materials that are particularly suitable for forming such regions include higher branched polymer particles, dendrimers, and crosslinked particles that can be prepared, for example, by emulsion polymerization. Crosslinked styrene based polymer particles having a particle size of less than 30 nm, more preferably less than 20 nm (preferably a copolymer of styrene with a second monomer having at least two ethylenically unsaturated groups, such as divinyl benzene or di- Isopropenyl benzene) is particularly suitable for use as porogen with the polymers of the invention as matrix material (see co-pending US applications 10 / 077,642 and 10 / with agent dock numbers 61599 and 61568, respectively). 077,646). Porogen may be added after the B-step, but porogen may be added to the monomer prior to the reaction of the B-step. In the latter case, porogens are believed to react with monomers without being bound by theory. However, whether chemical bonds are formed or other interactions occur, such as the formation of interpenetrating network structures, grafts are formed between the particles and the monomers / oligomers and detected by SEC analysis. Graftron means that the matrix is chemically bound to or permanently entangled with the porogen. If the mixture is not gelled, porogens can also be grafted to the material that has undergone the B-step if it is added after suitable b-step has already occurred slightly.

Preferably, for substrates applied with the films of the polymers of the invention, the film thickness is in the range of 50 to 1000 nm. For preferred porous films, the porosity is preferably 5 to 80%, more preferably greater than 10% and less than 70%, most preferably greater than 15% and less than 50%, and pore size is 5 to 30, preferably 5 To 20, more preferably 5 to 15 nm.

Example 1

Synthesis of Products Containing Monomers of Formula (II)

A. 4- Bromophenylacetyl Chloride synthesis

4-bromophenylacetic acid (99.5 g, 0.46 mol) and N, N-dimethylformamide (2 mL) were pre-dried 1 L glass monocyte round bottom Schlenk with magnetic stir bar pre-dried under dry nitrogen atmosphere To the reactor. The reactor is sealed under dry nitrogen and then placed on a Schlenk line under slightly positive nitrogen pressure. Thionyl chloride (300 mL) is added to a predried glass addition funnel equipped with a Schlenk adapter in a dry nitrogen atmosphere, then sealed under dry nitrogen and placed on a Schlenk line. After connecting the reactor and the addition funnel under dynamic nitrogen flow, thionyl chloride is added dropwise to the stirred reactor. While maintaining a nitrogen flow in the Schlenk reactor, gas from the reaction is introduced into the scrubbing facility through the Schlenk adapter on the addition funnel. When finished adding thionyl chloride, the addition funnel under dynamic nitrogen flow is replaced with a condenser covered with a Schlenk adapter entering the cleaning facility. The reactor contents are gently heated to 60 ° C. using a thermostatic heating mantle. After holding at 60 ° C. for 2.5 hours, excess thionyl chloride is removed from the product by applying vacuum from the Schlenk manifold until 60 ° C. and 159 microns are achieved. The resulting 4-bromophenylacetyl chloride product (105.95 g, 98.1% isolation yield) is stored under dry nitrogen until use.

B. 4,4'- Vis [(4- Bromophenyl ) Acetyl ] Synthesis of Phenyl Ether

Diphenyl ether (38.61 g, 0.227 mol), aluminum chloride (60.53 g, 0.454 mol) and anhydrous dichloromethane (250 mL) were pre-dried 1 liter glass monocyte round bottom Schlenk with magnetic stir bar pre-dried under dry nitrogen atmosphere To the reactor. The reactor is sealed under dry nitrogen and then placed on a Schlenk line under slightly positive nitrogen pressure. Then place an ice bath under the reactor. 4-bromophenylacetyl chloride (105.95 g, 0.454 mol) obtained in the above A dissolved in dichloromethane (100 mL) was added to a pre-dried glass addition funnel equipped with a Schlenk adapter under a dry nitrogen atmosphere, followed by dry nitrogen Underneath and placed on a Schlenk line. After connecting the reactor and the addition funnel under dynamic nitrogen flow, the 4-bromophenylacetyl chloride solution is added dropwise to the stirred reactor over 3 hours. Two hours after the reaction, the reactor is removed from the Schlenk line and the contents are poured onto crushed ice in a 4 L beaker. After the ice has dissolved, the precipitated product is dissolved in dichloromethane (14 L) and the aqueous layer is removed using a separatory funnel. The dichloromethane solution is washed with deionized water (2 L) and then dried over anhydrous sodium sulfate. The resulting slurry was filtered through an intermediate fritted glass funnel, and the dried filtrate was then passed through a silica gel column using further dichloromethane (2 L) as eluent. Dichloromethane solution was rotary evaporated to dryness to yield 119.1 g of white powder. High pressure liquid chromatography (HPLC) analysis demonstrates the presence of 94 area% of the desired product with 6 area% of a single by-product. Recrystallized from boiling acetonitrile (14 L) (cooled to room temperature and left for 16 hours), recovered through filtration and dried in a vacuum oven to give 96.0 g (75.0% isolation yield) of 4,4'-bis [ (4-Bromophenyl) acetyl] phenyl ether is obtained as shiny white plate crystals and is verified by HPLC analysis that by-products have been completely removed (100 area% of product). ¹ H nuclear magnetic resonance (NMR) analysis confirms the structure of the product.

C. 4,4'- Vis [(4- Bromophenyl ) Glyoxalyl ] Synthesis of Phenyl Ether

2 l with a glass mechanical stir bar with 4,4'-bis [(4-bromophenyl) acetyl] phenyl ether (95.5 g, 0.169 mol) and dimethylsulfoxide (1.8 l) obtained from B above with a teflon paddle Add to a glass three neck round bottom reactor. The reactor is further equipped with a thermometer with a chilled (2 ° C.) condenser and a thermostatic heating mantle entering the scrubber. Aqueous 48% hydrobromic acid (199.7 g) is added as a stream to the stirred slurry in the reactor over 3 minutes to induce exotherm to 45 ° C. Heating is then commenced at 100 ° C., once reaching 92 ° C., a clear bright orange solution is formed. After 2 hours at the reaction temperature of 100 ° C., the hot product solution is diluted in 8.2 L of toluene and the toluene solution is washed 5 times with 1.6 L of deionized water. The washed toluene solution was rotary evaporated to dryness to yield 99.2 g (99.1% isolated yield) of pale yellow powder. HPLC analysis demonstrates that the desired product is present at 100 area%. ¹ H NMR analysis confirms the structure of the product.

D. 4,4'- Vis [(4- Phenylethynylphenyl ) Glyoxalyl ] Synthesis of Phenyl Ether

4,4'-bis [(4-bromophenyl) glyoxalyl] phenyl ether (99.2 g, 0.1675 mol) obtained in the above C, phenylacetylene (41.37 g, 0.405 mol), triethyl sparged with dry nitrogen Amine (92.5 g, 0.914 mol), triphenylphosphine (2.22 g, 0.00847 mol), palladium (II) acetate (0.31 g, 0.00137 mol), and N, N-dimethylformamide (1063 ml) sparged with dry nitrogen ) Is added to a pre-dried 2 L glass three-neck round reactor with magnetic stir bar pre-dried under dry nitrogen atmosphere. The reactor is further equipped with a thermometer with a fan cooled spiral condenser and a thermostatically heated heating mantle. Stirring and heating are started and a clear pale yellow solution is formed after 13 minutes of reaching a temperature of 45 ° C. After a cumulative 1.2 hour the temperature of 80 ° C. is reached and thereafter maintained for 14.7 hours. At this time, HPLC analysis indicated that the 4,4'-bis [(4-bromophenyl) glyoxalyl] phenyl ether reactant was completely converted. The reactor contents are poured onto crushed ice in a pair of 4 L beakers. After the ice melts, the precipitated product is recovered by filtration through an intermediate fritted glass funnel. The product mass on the funnel was washed twice with 500 mL of deionized water and then recrystallized directly from boiling acetonitrile (22.5 L) to obtain a moist product. The recrystallization solution was cooled to room temperature and left for 16 hours to give 92.2 g (86.7% isolation yield) of 4,4'-bis [(4-phenylethynylphenyl) glyoxalyl] phenyl ether as pale yellow crystalline product. To obtain. HPLC analysis demonstrates that the desired product is present at 100 area%. NMR analysis and electron ionization mass spectrometer analysis (EI MS) confirm the structure of the product.

E. 3,3 '-(oxy-di-1,4-phenylene) -4,4'-bis [4-phenylethynylphenyl] -2,5-diphenylcyclopentadienone Synthesis of Product Containing Formula (II)

4,4'-bis [(4-phenylethynylphenyl) glyoxalyl] phenyl ether (11.05 g, 0.0174 mol), 1,3-diphenyl acetone (7.76 g, 0.0369 mol) obtained in the above D, anhydrous 1-propanol (1319 mL) and anhydrous toluene (70 mL), both sparged with dry nitrogen, are added to a pre-dried 2 L three-necked flask equipped with a magnetic stirrer under a dry nitrogen atmosphere. The reactor is further equipped with a thermometer with a chilled (2 ° C.) condenser and a thermostatically heated heating mantle. Stirring and heating are initiated and benzyltrimethylammonium hydroxide (40% in methanol, 1.86 g) is added when the solution reaches reflux, which immediately becomes dark reddish purple. After reflux for 30 minutes, HPLC analysis confirmed that the 4,4'-bis [(4-phenylethynylphenyl) glyoxalyl] phenyl ether reactant was completely converted. At this point, the heating is stopped and the heating mantle is removed from the reactor and the reaction mixture is cooled to room temperature. The product is recovered by filtration through an intermediate fritted glass funnel. The crystalline product on the funnel was washed twice with 50 ml of 1-propanol and then dried in a vacuum oven at 80 ° C. to yield 11.31 g (66.1% isolation yield) of 3,3 ′-(oxy-di-1, 4-phenylene) -4,4'-bis [4-phenylethynylphenyl] -2,5-diphenylcyclopentadienone (Formula II) is obtained as a dark reddish crystalline product. HPLC analysis demonstrates the presence of 75 area% of monomers of formula (II) with two trace byproducts. Electrospray ionization liquid chromatography mass spectrometry analysis (ESI LC MS) confirms that the structure of the peak of 75 area percent in HPLC analysis is of formula II.

Example 2

Synthesis of Monomers of Formula II

A. 4,4'- Vis [(4- Bromophenyl ) Glyoxalyl ] Synthesis of Phenyl Ether

2 l of 4,4'-bis [(4-bromophenyl) acetyl] phenyl ether (44 g, 0.078 mol) and dimethylsulfoxide (600 mL) prepared in a similar manner to that described in Example 1 B with a magnetic stirrer Add to a glass three neck round bottom reactor. Aqueous 48% hydrobromic acid (100 g) is added with additional funnel within 3 minutes. Then start heating to 90 ° C. and when this temperature is reached a clear bright orange solution is formed. After 3 hours at a reaction temperature of 90 ° C., the hot product solution is diluted in 3 L of toluene and the toluene solution is washed twice with 300 ml of deionized water. The washed toluene solution was rotary evaporated to dryness to yield 30 g (65% isolated yield) of pale yellow powder. HPLC analysis demonstrates that the desired product is present at 100 area%. ¹ H NMR analysis confirms the structure of the product.

B. 4,4'- Vis [(4- Phenylethynylphenyl ) Glyoxalyl ] Synthesis of Phenyl Ether

In a 500 ml flask, 29.6 g (0.05 mol) of 4,4'-bis [(4-bromophenyl) glyoxalyl] phenyl ether obtained in the above A, 29 g (0.29 mol) of triethylamine, and 12.2 g of phenylacetylene ( 0.12 mol) and 120 ml of N, N-dimethylformamide are added thereto. After purging the reaction mixture with nitrogen for 15 minutes, 0.60 g (0.0023 mol) of triphenylphosphine and 0.10 g (0.00045 mol) of palladium acetate are added. The reaction mixture is heated to 80 ° C. for 3 hours under a nitrogen atmosphere, then the flask is cooled to room temperature and water (200 mL) is added. The solid product is filtered off and dissolved in 2 liters of toluene. The organic solution is washed with 10% aqueous HCl solution and saturated aqueous NaCl solution and then dried over anhydrous Na ₂ SO ₄ . The toluene solution is then passed through a silica gel filter, toluene is removed and recrystallized from toluene / hexanes to give pure product (23.3 g, 73% isolation yield).

C. Formula II Monomeric synthesis

4,4'-bis [(4-phenylethynylphenyl) glyoxalyl] phenyl ether (12.7g, 0.0lmol) and 1,3-diphenylacetone (9.45g, 0.045mol) obtained in Example 2B. ) Is added to 300 ml of anhydrous 1-propanol. Stirring and heating are initiated and 1.5 ml of benzyltrimethylammonium hydroxide (40% in methanol, 3 ml) is added when the suspension reaches reflux temperature, which immediately becomes dark reddish purple. After maintaining reflux for 2 hours, HPLC analysis confirmed that the 4,4'-bis [(4-phenylethynylphenyl) glyoxalyl] phenyl ether reactant was completely converted. At this point, the oil bath is removed from the reactor and the reaction mixture is cooled to room temperature. The product is recovered by filtration through an intermediate fritted glass funnel. The crystalline product on the funnel was washed twice with 100 ml of 1-propanol and then dried in a vacuum oven to yield 16.1 g (91% isolation yield) of monomers having a purity> 91% by HPLC analysis.

Example 3

Synthesis of Monomers of Formula III

A. ethyl 4- Bromophenyl acetate synthesis

A solution of 63 g (0.29 mol) of 4-bromophenyl acetic acid and 50 ml of concentrated sulfuric acid in 500 ml of anhydrous ethanol was refluxed for 8 hours and then left overnight. After pouring over 600 g ice, the mixture is extracted with ether / hexane. The ether extract is washed well with water and the sodium bicarbonate solution is dried over anhydrous sodium sulfate. The solvent is removed by rotary evaporation to yield 57 g (0.24 mol, 80% isolation yield) of oil which crystallizes on cooling. Filtration and washing with hexanes give pure product.

B. γ -(4- Bromophenylaceto ) -α- Of phenylacetonitrile synthesis

Sodium (6.0 g, 0.26 mol) is added to 90 mL of absolute ethanol in a 250 mL three neck flask equipped with a stirrer, condenser and dropping funnel. 30.37 g (0.125 mol) of ethyl 4-bromophenyl acetate and benzyl cyanide (17.5 g, 0.15 mol) are added via a dropping funnel over 1 hour while stirring and refluxing the solution. The solution is refluxed for 3 hours, cooled and poured into 400 ml of cold water. The aqueous alkali solution is extracted three times with 100 ml of diethyl ether and the ether extract is decanted. The aqueous solution is acidified with cold 10% hydrochloric acid and then extracted three times with 100 ml of ether. The ether solution is extracted once with 100 ml of water, twice with 100 ml of 10% aqueous sodium bicarbonate solution and once with 100 ml of water and the aqueous extract is again decanted. The organic phase is dried over anhydrous sodium sulfate, filtered through a fluted filter and the ether is removed by rotary evaporation. The desired product (33 g) is recovered in 89% isolation yield.

C. 1- (4- Bromophenyl ) -3-phenyl-2- Propanon synthesis

In a 250 ml three-necked flask equipped with a stirrer and a condenser, 75 ml of 60% aqueous sulfuric acid solution and 30 g of acetonitrile derivative prepared in B were added. The mixture is heated to reflux with stirring until the release of carbon dioxide stops. The mixture is cooled, poured into 200 ml of ice water and extracted three times with 150 ml of diethyl ether. The ether extract is washed once with 50 ml of water, twice with 100 ml of 10% aqueous sodium hydroxide solution and then with 50 ml of water. Dry over anhydrous sodium sulfate, filter, and remove the ether by evaporation in vacuo to afford crude product. Recrystallization from 160 ml of hexane gave 11.5 g (42% isolation yield) of the product as a colorless solid.

D. 1- (4- Phenylethynylphenyl ) -3-phenyl-2- Propane synthesis

10.9 g (0.04 mol) 1- (4-bromophenyl) -3-phenyl-2-propanone, 10 g (0.10 mol) triethylamine, 4.6 g (0.045 mol) phenylacetylene in a 250 ml flask And 50 ml of N, N-dimethylformamide are added. The reaction mixture is purged with nitrogen for 15 minutes and then 0.47 g (0.0018 mol) triphenylphosphine and 0.067 g (0.0003 mol) palladium acetate are added. The reaction mixture is heated to 80 ° C. for 2 hours under a nitrogen atmosphere, then the flask is cooled to room temperature and water (200 mL) and diethyl ether (200 mL) are added. The resulting organic layer was washed with 10% aqueous HCl solution, water and saturated aqueous NaCl solution and then dried over anhydrous Na ₂ SO ₄ . The ether is removed and recrystallized from toluene / hexanes to give the pure product (8.5 g, 72% isolation yield).

E. Chemical Formula Ⅲ Monomeric synthesis

4,4'-bis (phenylglyoxalyl) phenyl ether (2.9 g, 0.0068 mol) and 4.0 g (0.0135) of 1- (4-phenylethynylphenyl) -3-phenyl-2-propanone obtained in the above D mol) is added to 100 ml of 1-propanol. Stirring and heating are initiated, and when the suspension reaches reflux temperature, benzyltrimethylammonium hydroxide (40% in methanol, 0.7 ml) is added and immediately becomes deep reddish purple. After maintaining reflux for 1 hour, HPLC analysis confirmed complete conversion of the 4,4'-bis (phenylglyoxalyl) phenyl ether reactant. At this point, the oil bath is removed from the reactor and the reaction mixture is cooled to room temperature. The product is recovered by filtration through an intermediate fritted glass funnel. The crystalline product on the funnel was washed twice with 100 ml of 1-propanol and then dried in a vacuum oven to give 6.1 g (93% isolation yield) of monomer III as a 1: 2: 1 mixture of the three isomers. To obtain.

Example 4

Synthesis of Monomers of Formula IV

A. 1,3- Vis (4- Bromophenyl )-2- Propane synthesis

To a suspension of sodium hydride (9.17 g, 0.23 mol) in 50 ml of toluene, a solution of ethyl 4-bromophenylacetate (50 g, 0.21 mol) in toluene (50 ml) is added dropwise at 30-32 ° C. After the addition is complete the reaction mixture is gradually warmed to 50 ° C. (the reaction begins to exotherm rapidly with the release of hydrogen gas). The reaction mixture is further heated to 78 ° C. for 2 hours, cooled to room temperature and the solution is neutralized by the slow dropwise addition of HCl (45 g) in water (22.5 g). The layers are separated and the aqueous phase is extracted with diethyl ether. The combined organic extracts are dried and the solvent is removed leaving a yellow oil. This oil is refluxed for 24 hours in a mixture of glacial acetic acid (60 mL) and concentrated HCl (30 mL). After cooling, the layers are separated and the organic layer solidifies to yield a yellow solid. This crude product is recrystallized from n-heptane to give the pure product as a white solid (31.2 g, 82% isolation yield).

B. 1,3- Vis (4- Phenylethynylphenyl )-2- Propane synthesis

18.4 g (0.05 mol) 1,3-bis (4-bromophenylphenyl) -2-propanone, 24 g (0.24 mol) triethylamine, 12 g (0.12 mol) phenylacetylene in a 250 ml flask, and Add 60 ml of N, N-dimethylformamide. The reaction mixture is purged with nitrogen for 15 minutes and then 0.60 g (0.0023 mol) triphenylphosphine and 0.08 g (0.00036 mol) palladium acetate are added. The reaction mixture is heated to 80 ° C. for 20 hours under a nitrogen atmosphere, then the flask is cooled to room temperature and water (200 mL) and toluene (200 mL) are added. The resulting organic layer was washed with 10% aqueous HCl solution, water and saturated aqueous NaCl solution and then dried over anhydrous Na ₂ SO ₄ . Toluene is removed and recrystallized from toluene / hexanes to give pure product (14.5 g) in an isolation yield of 71%.

C. Chemical Formula Ⅳ Monomeric synthesis

4,4'-bis (phenylglyoxalyl) phenyl ether (TK-1, 4.4 g, 0.01 mol) and 1,3-bis (4-phenylethynylphenyl) -2-propanone obtained in B above 8.2 g (0.02 mol) is added to the reactor containing 200 ml of anhydrous 1-propanol. Stirring and heating are initiated and benzyltrimethylammonium hydroxide (twice in 40%, 1.0 mL, 0.5 mL aliquots in methanol) is added when the suspension reaches reflux and immediately becomes deep reddish purple. After maintaining reflux for 2 hours, HPLC analysis confirmed complete conversion of 4,4'-bis (phenylglyoxalyl) phenyl ether reactant. At this point, the oil bath is removed from the reactor and the reaction mixture is cooled to room temperature. The product is recovered by filtration through an intermediate fritted glass funnel. The crystalline product on the funnel was washed twice with 100 ml of 1-propanol and dried in a vacuum oven to yield 10.3 g (87% isolation yield) of the monomer of formula IV.

Example 5

Synthesis of Non-ether Bonded Monomers of Formula (VII)

A. Potassium 1,3- Phenylene diacetate Through 1,3- Phenylenediacetyl Chloride synthesis

Potassium hydroxide (99.99%) (7.41 g, 0.132 mol) is added to deionized water (300 mL) and stirred to form a solution. 1,3-phenylenediacetic acid (11.65 g, 0.06 mol, 0.12-COOH equiv) is added to the aqueous potassium hydroxide solution and the slurry is gently heated until a solution is formed. The resulting solution is dried by rotary evaporation and then dried in a vacuum oven at 80 ° C. and 1 mm Hg for 16 hours. Dry further on a high vacuum line at 24 ° C. until a vacuum of 400 millitorr is reached. The white solid product (16.0 g) is recovered and kept under dry nitrogen atmosphere. In a dry nitrogen glove box, dipotassium salt is placed in a 500 ml monocyte round bottom Schlenk flask with a magnetic stir bar. All glassware and devices used in the glove box are pre-dried to remove moisture. Then anhydrous dichloromethane (100 mL) is added. The reactor is sealed under dry nitrogen and then removed from the glove box and placed on a Schlenk line under slightly positive nitrogen pressure. Thionyl chloride (100 g) is added to a glass addition funnel equipped with a Schlenk adapter under a dry nitrogen atmosphere, then sealed and placed on a Schlenk line. After connecting the reactor and the addition funnel under dynamic nitrogen flow all thionyl chloride is added to the stirred slurry in the reactor over 24 minutes. After an additional 55 minutes, N, N-dimethylformamide (0.35 mL) is injected into a fine white stirred slurry. During the entire reaction, gas from the reaction is introduced into the cleaning facility through the Schlenk adapter on the addition funnel while maintaining a dynamic nitrogen flow in the Schlenk reactor. After an additional 83 minutes, the reactor is sealed under nitrogen and placed in a glove box. Gently heat the reactor contents to 30 ° C. using a thermostatic heating mantle and apply excess vacuum from the product by applying vacuum from the glove box vacuum line until 30 ° C. and 710 millitorr is achieved. Remove it. The product in the reactor was extracted three times with anhydrous (chromatically purified on alumina under dry nitrogen) diethyl ether (100 mL) and each extract was passed through an intermediate fritted glass funnel to 1 L monocyte round bottom Schlenk with a magnetic stir bar. Put in the flask. The reactor contents are gently heated to 30 ° C. using a thermostatic heating mantle and vacuum is applied from the glove box vacuum line until reaching 32 ° C. and 730 millitorr to remove the diethyl ether solvent from the combined extracts. The resulting 1,3-phenylenediacetyl chloride (13.0 g, 0.0562 mol, 0.1125-COCl equiv., Isolation yield of 93.7%) is stored under dry nitrogen until use.

B. 1,3- Vis [(4- Bromophenyl ) Acetyl ] Synthesis of Benzene

In a dry nitrogen glove box, bromobenzene (157.0 g, 1.0 mol) is added to the reactor containing 1,3-phenylenediacetyl chloride (13.0 g, 0.0562 mol, 0.1125 COCl equivalents) obtained in A above. Stirring is initiated and aluminum chloride (18.0 g, 0.135 mol) is added to the stirred solution in 0.5 g aliquots every three minutes. After the addition of aluminum chloride, the dark amber stirred solution is maintained at 24 ° C. for 1 hour and then analyzed by HPLC. HPLC analysis confirmed complete conversion of 1,3-phenylenediacetyl chloride. The reactor is removed from the glove box and the contents are poured into crushed ice in a 4 L beaker. After the ice has dissolved, the precipitated product is dissolved in dichloromethane (1 L) and the aqueous layer is removed using a separatory funnel. The dichloromethane solution is washed with deionized water (500 mL) and then dried over anhydrous sodium sulfate. The resulting slurry was filtered through an intermediate fritted glass funnel, and the dried filtrate was then rotary evaporated to yield 30.2 g of yellow powder (still wet with bromobenzene). Recrystallization from boiling acetonitrile (cooled to room temperature and held for 16 hours) yielded 17.54 g (0.0372 mol, 66.1% isolation yield) of 1,3-bis [(4-bromophenyl) acetyl] benzene, HPLC analysis confirmed complete removal of impurities (100 area% of product). The acetonitrile filtrate is cooled to yield more 2.1 g of product.

C. 1,3- Vis [(4- Bromophenyl ) Glyoxalyl ] Synthesis of Benzene

1,3-bis [(4-bromophenyl) acetyl] benzene (17.54 g, 0.0372 mol) and dimethyl sulfoxide (473 mL) obtained in B were added to a 1 L glass three-neck round bottom reactor with magnetic stir bar. do. The reactor is further equipped with a thermometer with a chilled (2 ° C.) condenser and a thermostatically heated heating mantle. Aqueous 48% hydrobromic acid (43.8 g) is added as a stream to the stirred slurry in the reactor over 1 minute to induce exotherm to 37 ° C. Then start heating to 100 ° C. and once reaching 72 ° C. a clear bright amber solution is formed. After 2.8 hours at a reaction temperature of 100 ° C., the hot pale yellow slurry is diluted in 3.4 L of toluene and the toluene solution is washed five times with 400 ml of deionized water. The washed toluene solution is rotary evaporated to dryness and then further dried in a vacuum oven (80 ° C. and 1 mm Hg) to yield 18.7 g (100% isolated yield) of pale yellow crystalline powder. HPLC analysis demonstrates that the desired product is present at 100 area%.

D. 1,3- Vis [(4- Phenylethynylphenyl ) Glyoxalyl ] Synthesis of Benzene

1,3-bis [(4-bromophenyl) glyoxalyl] benzene (8.7 g, 0.0174 mol, 0.0348 Br-equivalent) obtained in the above C, phenylacetylene (4.30 g, 0.0421 mol), triethylamine ( 9.61 g, 0.095 mol), triphenylphosphine (0.23 g, 0.00088 mol), palladium (II) acetate (0.032 g, 0.00014 mol) and N, N-dimethylformamide (174 mL) were pre-dried under a dry nitrogen atmosphere To a predried 2 L glass three-neck round bottom reactor with magnetic stir bar. Triethylamine and N, N-dimethylformamide are sparged with dry nitrogen before use. The reactor is further equipped with a fan cooled spiral condenser and a thermometer with a thermostatically heated heating mantle. Stirring and heating are initiated and a clear bright amber solution is formed after reaching a temperature of 78 ° C. after 24 minutes. After 47 minutes cumulative, a temperature of 80 ° C. is reached and thereafter maintained for 19.5 hours. At this point, HPLC analysis confirmed the complete conversion of the 1,3-bis [(4-bromophenyl) glyoxalyl] benzene reactant. Pour the reactor contents onto crushed ice in a 4 L beaker. After the ice melts, it is dissolved in 2 liters of deionized water and the precipitated product is recovered by filtration through an intermediate fritted glass funnel. The mass of product on the funnel is washed with 200 mL of deionized water, and then a portion of the product is analyzed by HPLC to prove that the desired product is present at 91.6 area%. Boil as a slurry in acetonitrile (1.8 L), then hold for 18 hours at room temperature under stirring, filter on an intermediate fritted glass funnel and dry in a vacuum oven (40 ° C. and 1 mm Hg) to 8.55 g (90.6) 1,3-bis [(4-phenylethynylphenyl) glyoxalyl] benzene in% isolation yield) is recovered as a pale yellow solid. HPLC analysis demonstrates that the desired product is present at 100 area%. Confirm the structure of the product with EI MS.

E. 3,3 '-(1,3-phenylene) -4,4'-bis [(4-phenylethynyl) phenyl] -2,5-diphenylcyclopentadienone (Non-ether bonded Monomer ) (Formula Ⅶ ) Synthesis

1,3-bis [(4-phenylethynylphenyl) glyoxalyl] benzene (8.47 g, 0.0156 mol) obtained in the above D, 1,3-diphenylacetone (6.96 g, 0.0331 mol), anhydrous 1- Propanol (1400 mL) and anhydrous toluene (80.5 mL), both sparged with dry nitrogen, are added to a pre-dried 2 liter glass three-neck round bottom reactor equipped with a magnetic stirrer pre-dried under a dry nitrogen atmosphere. The reactor is further equipped with a fan cooled spiral condenser and a thermostatically heated heating mantle that uses a thermocouple to directly read the heating mantle surface temperature. Stirring and heating are initiated, and when a refluxing clear pale yellow solution is formed, benzyltrimethylammonium hydroxide (40% in methanol) (1.43 g) is added and immediately becomes a dark red solution. After reflux for 45 minutes, HPLC analysis confirmed that the 1,3-bis [(4-phenylethynylphenyl) glyoxalyl] benzene reaction was completely converted. At this point, after removing the heating mantle from the reactor, the stirred contents are then held at 24 ° C. for 18 hours. The product is recovered by filtration through an intermediate fritted glass funnel. The crystalline product on the funnel was washed twice with 20 ml of 1-propanol and then dried in a vacuum oven to give 12.60 g (90.6% isolated yield) of 3,3 '-(1,3-phenylene) -4 , 4'-bis [(4-phenylethynyl) phenyl] -2,5-diphenylcyclopentadienone (Formula X) is obtained as a dark reddish crystalline product.

Example 6

B-step of a product containing the monomer of Formula II of Example 1 and the monomer of Formula II of Example 2

In a dry nitrogen glove box, a portion (5.94 g) of the product containing the monomer of formula (II) obtained in Example 1 E (sprayed with dry nitrogen) was loaded with a 17 mm starhead TFE magnetic stirrer. Add to a ml glass three neck round bottom reactor. The reactor is further equipped with a thermometer with a fan cooled spiral condenser and a thermostatically heated heating mantle. The heating mantle surface further has a thermocouple for direct reading of the surface temperature. Agitation is initiated and a sample of homogeneous slurry is taken for gel permeation chromatography (GPC). All GPC analyzes are performed using tetrahydrofuran and polystyrene calibration standards as eluent. Heating is initiated and after 38 minutes a temperature of 200 ° C. is reached and maintained. The heating mantle surface temperature should maintain a 200 ° C. internal temperature for the B-step reaction in the range of 207 ° C. to 214 ° C. Samples of solutions are taken after 4, 6 and 7.5 hours of the B-step reaction and analyzed by GPC to obtain the following results.

At 7.5 hours of B-step time, the reaction is stopped due to viscosity building which makes proper agitation impossible. In all samples there is no gel visible to the naked eye.

In a similar manner, a portion of the monomer obtained in Example 2C (4.0 g) and mesitylene (9.3 g) are mixed and heated to reflux temperature (˜170 ° C.) under nitrogen. Samples of the solution are taken 2, 5, 12, 21, 26, 30 hours after the B-step reaction and analyzed by GPC to obtain the following results. All GPC analyzes are performed using tetrahydrofuran and polystyrene calibration standards as eluent.

Example 7

Differential Scanning Calorimeter of Monomers of Formula (II)

Differential Scanning Calorimetry (DSC) is performed using 3.2 and 3.0 mg of the monomer of Formula II obtained in Example 2C, respectively. DSC 2910 Modular DSC (TA Instruments) is used and a heating rate of 7 ° C./min from 25 ° C. to 400 ° C. under a nitrogen flow stream of 45 cm 2 / min. The results are shown as mean values obtained from a pair of analyzes. Single endothermic transitions are minimally observed at 240.9 ° C. (13.55 joules / g). A single exothermic transition that can contribute to the Diels-Alder reaction of the phenylethynyl group and cyclopentadienone group is observed at 254.0 ° C. (158.0 joules / g) at maximum. The onset temperature for exothermic transition is 242.0 ° C and the termination temperature is 285.3 ° C. Secondary scans using the conditions described above showed no glass transition temperature or any other transition. The sample recovered from the DSC analysis is a hard pale yellow fused transparent solid.

Example 8

Differential Scanning Calorimetry of Non-ether Bonded Monomers of Formula (VII)

Differential Scanning Calorimetry (DSC) is performed using 4.2 and 4.0 mg of the non-ether bound monomers obtained in Example 5E, respectively. DSC 2920 Modular DSC (TA Instruments) is used and a heating rate of 7 ° C./min from 25 ° C. to 500 ° C. under a nitrogen flow stream of 45 cm 2 / min. The results are shown as averages obtained from a pair of analyzes. Single exothermic transitions are observed at a maximum at 351.2 ° C. (169.3 joules / g). The onset temperature for the exothermic transition is 308.8 ° C and the termination temperature is 384.1 ° C. Secondary scans using the conditions described above showed no glass transition temperature or any other transition. The sample recovered from the DSC analysis is an unmelted powdery solid.

Example 9

TICA experiment to measure the count profile of a sample that has undergone a B-step

The coefficient profile during curing of the B-staged monomer (with or without porogen) of the type disclosed in Example 1 E is determined by evaluating the composition using torical impregnated cloth analysis (TICA). In this technique, a glass fabric (18x6.4x0.40mm) is installed in a dynamic machine analyzer such as TA DMA 2980. The end of the fabric is wrapped in aluminum foil, leaving a length of 18 mm exposed. The fabric is then placed on a vertical clamp of a dynamic machine analyzer and the pipette is infiltrated with a solution containing 10-30% solids concentration of the B-staged oligomer. Completely wet the fabric and use a pipette to remove excess solution. Heat heaters and ovens are fitted and a nitrogen flow of about 3 standard square feet / hour is established. The sample is heated to 430 ° C. at 7 ° C./min and held for 40 minutes before cooling. Data analysis is performed to determine the temperature vs. bending coefficient for the composite of glass and composition. TICA data in both B-staged monomers and B-staged monomer samples with porogens show that the solution is plasticized by solvent to give a mixture with very low coefficients. Initial heating and solvent evaporation maintain the same free count profile until the temperature reaches 200 ° C., after which the count begins to increase due to the Diels-Alder reaction of the phenylacetylene and cyclopentadienone groups. The glass thermosetting coefficient, which becomes even upon curing, is completed at 300 ° C. As shown in the TICA plot, there is no increase or decrease of the modulus after 300 ° C.

Example 10

Preparation of Porous Matrix from Monomer and Crosslinked Polystyrene Porogens of Formula (II)

A. 20% 26 nm crosslinked polystyrene porogen

In a 50 ml round bottom flask, 4 g of monomer of formula (II), crosslinked polystyrene nanoparticles (average particle size 26 nm, measured by size exclusion chromatography using a laser light scattering detector, co-pending application No. 61599 ) 1.0 g and 9.3 g of γ-butyrolactone (GBL) are prepared. The resulting mixture is purged with nitrogen for 15 minutes and then heated to 200 ° C. using an oil bath for 8 hours under nitrogen. The mixture is then cooled to 145 ° C. and diluted with the same amount of cyclohexanone. The mixture is finally cooled to room temperature to give a 17.5% polymer mixture in GBL / cyclohexanone. Analysis of the final mixture by GPC showed Mn = 3,588 and Mw = 24,905 for polystyrene standards and the graft ratio (ie matrix weight grafted with porogen divided by weight of porogen) was 0.24.

The mixture is applied to a silicon wafer and cast by spin-coating to form a 1.0 micron thick film. The film is baked for 2 minutes on an MTI hotplate at 150 ° C. and then the applied wafers are transferred to a vacuum oven. The oven temperature was raised to 430 ° C. at 7 ° C./min under nitrogen and held for 40 minutes to decompose and cool the polystyrene porogen. Estimates of average spherical pore size based on visual observation of a transmission electron microscope (TEM) of the film have a pore size in the range of 8-36 nm with a diameter of about 20 nm. The refractive index of the resulting film is 1.52.

B. 30% 26 nm crosslinked polystyrene porogen

4 g of monomer of Formula II, crosslinked polystyrene nanoparticles (average particle size 26 nm as measured by size exclusion chromatography using a laser light scattering detector, prepared from microemulsion polymerization) in a 50 ml round bottom flask and 9.3 g of GBL Add. The resulting mixture is purged with nitrogen for 15 minutes and then heated to 200 ° C. using an oil bath for 6 hours under nitrogen. The mixture is then cooled to 145 ° C. and diluted with the same amount of cyclohexanone. The mixture is further cooled to room temperature to give a 17.5% polymer mixture in GBL / cyclohexanone. Analysis of the final mixture by GPC showed Mn = 3,100 and Mw = 19,600 with a graft ratio of 0.19 for polystyrene standards.

The mixture is applied to a silicon wafer and cast by spin-coating to form a film 1.0 micron thick. The film is baked for 2 minutes on an MTI hotplate at 150 ° C. and then the applied wafers are transferred to a vacuum oven. The oven temperature was raised to 430 ° C. at 7 ° C./min under nitrogen and held for 40 minutes to decompose and cool the polystyrene porogen. The estimate of the average spherical pore size based on visual observation of the TEM of the film has a diameter of about 19 nm and a pore size in the range of 4 to 33 nm. The resulting film has a refractive index of 1.46 and a dielectric constant of 2.14.

C. 30% 30 nm crosslinked polystyrene porogen

In a 50 ml round bottom flask, 4 g of monomer of formula II, crosslinked polystyrene nanoparticles (average particle size 30 nm as measured by size exclusion chromatography using a laser light scattering detector, prepared from microemulsification polymerization) and 9.3 g of GBL Add. The resulting mixture is purged with nitrogen for 15 minutes and then heated to 200 ° C. using an oil bath for 6 hours under nitrogen. The mixture is then cooled to 145 ° C. and diluted with the same amount of cyclohexanone. The mixture is further cooled to room temperature to give a 17.5% polymer mixture in GBL / cyclohexanone. Analysis of the final mixture by GPC showed Mn = 3,100 and Mw = 38,800 with a graft ratio of 0.19 for polystyrene standards.

The mixture is applied to a silicon wafer and cast by spin-coating to form a film of ˜1.0 micron thick. The film is baked for 2 minutes on an MTI hotplate at 150 ° C. and then the applied wafers are transferred to a vacuum oven. The oven temperature was raised to 430 ° C. at 7 ° C./min under nitrogen and held for 40 minutes to decompose and cool the polystyrene porogen. Estimates of average spherical pore size based on visual observation of the TEM of the film have a pore size of about 20 nm in diameter and in the range of 6 to 32 nm. The refractive index of the resulting film is 1.47 and the dielectric constant is 2.13.

D.30% 25 nm crosslinked polystyrene porogen

4 g of monomer of Formula II, crosslinked polystyrene / 10% poly (tert-butylstyrene) nanoparticles (50 nm round bottom flask, average particle size 25 nm, microemulsification measured by size exclusion chromatography using a laser light scattering detector) 1.72 g and 9.3 g GBL are added. The resulting mixture is purged with nitrogen for 15 minutes and then heated to 200 ° C. using an oil bath for 8 hours under nitrogen. The mixture is then cooled to 145 ° C. and diluted with the same amount of cyclohexanone. The mixture is further cooled to room temperature to give a 17.5% polymer mixture in GBL / cyclohexanone. Analysis of the final mixture by GPC showed Mn = 3,200 and Mw = 19,800 with a graft ratio of 0.21 for polystyrene standards.

The mixture is applied to a silicon wafer and cast by spin-coating to form a film 1.0 micron thick. The film is baked for 2 minutes on an MTI hotplate at 150 ° C. and then the applied wafers are transferred to a vacuum oven. The oven temperature was raised to 430 ° C. at 7 ° C./min under nitrogen and held for 40 minutes to decompose and cool the polystyrene porogen. Estimates of average spherical pore size based on visual observation of the TEM of the film have a diameter of about 19 nm and a pore size in the range of 4 to 35 nm. The resulting film has a refractive index of 1.46 and a dielectric constant of 2.11.

E. 30% 13 nm crosslinked polystyrene porogen

4 g of monomer of Formula II, crosslinked polystyrene nanoparticles (average particle size 13 nm measured by size exclusion chromatography using a laser light scattering detector, prepared from microemulsion polymerization) in a 50 ml round bottom flask and 9.3 g of GBL Add. The resulting mixture is purged with nitrogen for 15 minutes and then heated to 200 ° C. using an oil bath for 6 hours under nitrogen. The mixture is then cooled to 145 ° C. and diluted with the same amount of cyclohexanone. The mixture is further cooled to room temperature to give a 17.5% polymer mixture in GBL / cyclohexanone. Analysis of the final mixture by GPC showed Mn = 43,000 and Mw = 82,600 and a graft ratio of 0.37 for polystyrene standards.

The mixture is applied to a silicon wafer and cast by spin-coating to form a film 1.0 micron thick. The film is baked for 2 minutes on an MTI hotplate at 150 ° C. and then the applied wafers are transferred to a vacuum oven. The oven temperature was raised to 430 ° C. at 7 ° C./min under nitrogen and held for 40 minutes to decompose and cool the polystyrene porogen. Estimates of average spherical pore size based on visual observation of the TEM of the film have a diameter of about 12 nm and a pore size in the range of 5-18 nm. The resulting film has a refractive index of 1.47 and a dielectric constant of 2.12.

F. 35% 26 nm crosslinked polystyrene porogen

4 g of monomer of Formula II, crosslinked polystyrene nanoparticles (average particle size 26 nm as measured by size exclusion chromatography using a laser light scattering detector, prepared from microemulsion polymerization) in a 50 ml round bottom flask and 9.3 g of GBL Add. The resulting mixture is purged with nitrogen for 15 minutes and then heated to 200 ° C. using an oil bath for 6 hours under nitrogen. The mixture is then cooled to 145 ° C. and diluted with the same amount of cyclohexanone. The mixture is further cooled to room temperature to give a 17.5% polymer mixture in GBL / cyclohexanone. Analysis of the final mixture by GPC showed Mn = 3,200 and Mw = 39,400 and a graft ratio of 0.24 for polystyrene standards.

The mixture is applied to a silicon wafer and cast by spin-coating to form a film 1.0 micron thick. The film is baked for 2 minutes on an MTI hotplate at 150 ° C. and then the applied wafers are transferred to a vacuum oven. The oven temperature was raised to 430 ° C. at 7 ° C./min under nitrogen and held for 40 minutes to decompose and cool the polystyrene porogen. Estimates of average spherical pore size based on visual observation of the TEM of the film have a pore size of about 21 nm in diameter and in the range of 7 to 37 nm. The resulting film has a refractive index of 1.43 and a dielectric constant of 1.98.

Example 11

Preparation of Porous Matrix from Monomers of Formula III and Crosslinked Polystyrene Porogens

4 g of monomer of Formula III, 1.72 g of cross-linked polystyrene nanoparticles (average particle size 26 nm as measured by size exclusion chromatography using a laser light scattering detector, prepared from microemulsion polymerization) in a 50 ml round bottom flask and γ-buty Add 9.3 g of rockactone (GBL). The resulting mixture is purged with nitrogen for 15 minutes and then heated to 200 ° C. using an oil bath for 6 hours under nitrogen. The mixture is then cooled to 145 ° C. and diluted with the same amount of cyclohexanone. The mixture is further cooled to room temperature to give a 17.5% polymer mixture in GBL / cyclohexanone.

The mixture is applied to a silicon wafer and cast by spin-coating to form a film 1.0 micron thick. The film is baked for 2 minutes on an MTI hotplate at 150 ° C. and then the applied wafers are transferred to a vacuum oven. The oven temperature was raised to 430 ° C. at 7 ° C./min under nitrogen and held for 40 minutes to decompose and cool the polystyrene porogen. Estimates of average spherical pore size based on visual observation of the TEM of the film have a diameter of about 20 nm and a pore size in the range of 6 to 33 nm. The resulting film has a refractive index of 1.46 and a dielectric constant of 2.19.

Example 12

Preparation of Porous Matrix from Monomer and Crosslinked Polystyrene Porogens of Formula (IV)

30% 13nm crosslinked polystyrene porogen

4 g of monomer of Formula IV, crosslinked polystyrene nanoparticles (average particle size 13 nm measured by size exclusion chromatography using a laser light scattering detector, prepared from microemulsion polymerization) in a 50 ml round bottom flask and γ-buty Add 9.3 g of rockactone (GBL). The resulting mixture is purged with nitrogen for 15 minutes and then heated to 200 ° C. using an oil bath for 2 hours under nitrogen. The mixture is then cooled to 145 ° C. and diluted with the same amount of cyclohexanone. The mixture is further cooled to room temperature to give a 17.5% polymer mixture in GBL / cyclohexanone.

The mixture is applied to a silicon wafer and cast by spin-coating to form a film 1.0 micron thick. The film is baked for 2 minutes on an MTI hotplate at 150 ° C. and then the applied wafers are transferred to a vacuum oven. The oven temperature was raised to 430 ° C. at 7 ° C./min under nitrogen and held for 40 minutes to decompose and cool the polystyrene porogen. Estimates of average spherical pore size based on visual observation of the TEM of the film have a diameter of about 10 nm and a pore size in the range of 6 to 19 nm. The resulting film has a refractive index of 1.45 and a dielectric constant of 2.15.

Example 13

Synthesis of High Purity Monomers of Formula II

A. High purity 4,4'- Vis [(4- Bromophenyl ) Acetyl ] Synthesis of Phenyl Ether

Diphenyl ether (200.96 g, 1.1805 mol), aluminum chloride (321.15 g, 2.409 mol) and anhydrous 1,2-dichloroethane (2.1 L) were pre-dried 5 L glass with magnetic stir bar pre-dried under dry nitrogen atmosphere It is added to a three-neck round bottom reactor. The reactor is sealed under dry nitrogen and then placed on a Schlenk line under slightly positive nitrogen pressure. Place ice and salt bath under the reactor 25 minutes before starting the reaction. 4-Bromophenylacetyl chloride (556.26 g, 2.361 mol) prepared by the method of Example 1 A was added to a pre-dried glass addition funnel with a Schlenk adapter under a dry nitrogen atmosphere, sealed under dry nitrogen, and Schlenk Place it on the line. After connecting the reactor and the addition funnel under dynamic nitrogen flow, the 4-bromophenylacetyl chloride solution is added dropwise to the stirred reactor over 3.7 hours. Two hours after the reaction has passed, magnetic agitation is stopped and the central port of the reactor is opened to insert a glass stirring shaft with a Teflon paddle and attached to a variable speed motor to effect mechanical agitation of the reactor contents. Open the second port and install an additional funnel containing cold deionized water. At the same time as mechanical agitation, the dropwise addition of cold deionized water is initiated and the first few drops of water are added to induce lump precipitation of the pale yellow product. Water is added continuously until all red orange color disappears and a stirred slurry of white solid in purple liquid remains. The stirred slurry is maintained until cooled to 23 ° C., at which point filtration through a coarse fritted glass funnel is initiated. The white powder layer packed on the filter is washed with deionized water and then separated and divided into approximately equal amounts of 6 and then washed in a Waring blender with 250 ml of deionized water for one. The washed product was recovered by filtration with an intermediate fritted glass funnel and dried in a vacuum oven at 80 ° C. to 498.3 g (74.8% isolation yield) of 4,4′-bis [(4-bromophenyl) acetyl] phenyl Obtain ether. HPLC analysis confirms that the target product is present at 100 area%.

B. High purity 4,4'- Vis [(4- Bromophenyl ) Glyoxalyl ] Synthesis of Phenyl Ether

5 L with a glass mechanical stir bar with a Teflon paddle of 4,4'-bis [(4-bromophenyl) acetyl] phenyl ether (212.48 g, 0.3766 mol) and dimethyl sulfoxide (3.1 L) obtained in A Add to a glass three neck round bottom reactor. The reactor is further equipped with a condenser (not chilled) and a thermometer which enters the cleaning plant. Aqueous 48% hydrobromic acid (444.4 g) is added to the stirred slurry in the reactor over 32 minutes to induce exotherm to 39 ° C. The thermostatic heating mantle is placed under the reactor and begins to heat mildly to 100 ° C. over 3.2 hours, when reaching 75 ° C. a clear bright amber solution is formed. Upon reaching 92 ° C., a pale yellow slurry is formed. After 2.8 hours at a reaction temperature of 100 ° C. the hot product solution is diluted with 12.7 L of deionized water, then stirred as slurry for 16 hours and then filtered on a coarse fritted glass funnel. The pale yellow powder layer packed on the filter was washed with deionized water and then removed and dried in a vacuum oven at 100 ° C. to 222.09 g (99.6% isolation yield) of 4,4′-bis [(4-bromophenyl) Glyoxalyl] phenyl ether is obtained. HPLC analysis confirmed the presence of the desired product at 100 area%.

C. High purity 4,4'- Vis [(4- Phenylethynylphenyl ) Glyoxalyl ] Synthesis of Phenyl Ether

4,4'-bis [(4-bromophenyl) glyoxalyl] phenyl ether (266.51 g, 0.45 mol), phenylacetylene (16.67 g, 0.1632 mol) prepared by the method of B was sparged with dry nitrogen N, N-dimethylformamide (2854.5) sprayed with triethylamine (248.6 g, 2.457 mol), triphenylphosphine (5.97 g, 0.2276 mol), palladium (II) acetate (0.83 g, 0.0037 mol) and dry nitrogen g) is added to a 5 L glass three-neck round bottom reactor pre-dried under a dry nitrogen atmosphere. The reactor is further equipped with a glass stirring shaft with an addition funnel loaded with a fan cooled helical condenser, a thermometer with a thermostatically heated heating mantle, and a Teflon paddle coupled to a variable speed motor to provide mechanical agitation. Additional phenylacetylene (94.45 g, 0.9247 mol) is added to the addition funnel. 25 minutes after the start of stirring and heating, a clear bright amber solution is formed when the temperature reaches 47 ° C. After a cumulative 1.85 hours, a temperature of 80 ° C. was reached and the dropwise addition of phenylacetylene was initiated and completed after 2.3 hours. After 17 hours cumulative, HPLC analysis confirmed that the 4,4'-bis [(4-bromophenyl) glyoxalyl] phenyl ether reactant was completely converted and the presence of monobromonophenylethynyl intermediate was not detected. do. At this point, the addition funnel is filled with deionized water (450 mL) and added dropwise to the stirred solution while maintaining a temperature of 80 ° C. After the addition of water, the heating is stopped and the stirred solution is slowly cooled, crystallized and filtered through a coarse fritted glass funnel. The yellow powder layer packed on the filter was washed with deionized water and then removed and dried in a vacuum oven at 100 ° C. to 257.32 g (90.1% isolation yield) of 4,4′-bis [(4-phenylethynylphenyl ) Glyoxalyl] phenyl ether. HPLC analysis confirmed the presence of the desired product at 100 area%.

D. High Purity 3,3 '-(oxy-di-1,4-phenylene) -4,4'-bis [4-phenylethynylphenyl] -2,5-diphenylcyclopentadienone Synthesis of Formula (II)

4,4'-bis [(4-phenylethynylphenyl) glyoxalyl] phenyl ether (100.08 g, 0.1577 mol), 1,3-diphenylacetone (74.61 g, 0.3548 mol) obtained in the above C. 2 Propanol (1334 mL) and toluene (1001 mL) are added to a 5 L four-neck Morton flask. The reactor was a chilled (2 ° C.) condenser, a thermometer with a thermostatically heated heating mantle, a Claisen adapter with an addition funnel and a nitrogen sparge tube, and a turbine-type Teflon stirrer coupled to a variable speed motor to provide mechanical agitation. It is further provided with the glass stirring shaft which has a. The addition funnel is charged with 1M tetrabutylammonium hydroxide (8.34 mL) in methanol dissolved in 2-propanol (166.4 mL) under a dry nitrogen atmosphere. After stirring and sparging with nitrogen (1 L / min), heating is started and when the stirred slurry reaches 80 ° C., the sparging tube is removed and replaced with an overhead inlet for nitrogen. The solution in the addition funnel starts to add to the reflux stirred slurry and is completed over 33 minutes, during which the yellow slurry turns to a deep red solution. 40 minutes after the addition of the catalyst solution, the red solution turns into a cloudy red slurry and has signs of granular precipitation at the glass-liquid boundary in the reactor. HPLC analysis at this point confirms the optimal conversion of the desired product and the formation of minimal by-products while simultaneously converting the 4,4'-bis [(4-phenylethynylphenyl) glyoxalyl] phenyl ether reactant. After a further 12 minutes, heating is stopped and the heating mantle is removed from the reactor, additional 2-propanol (1.5 L) is added to the reactor and the reaction mixture is cooled to room temperature using a cooling fan outside the reactor. When the stirred slurry reaches 24 ° C., the product is recovered by filtration through a coarse fritted glass funnel. The crystalline product on the funnel is washed with 2-propanol (200 mL) and then dropped back into the reactor washed with 2-propanol. Additional 2-propanol (1.2 L) was added to the reactor, then stirred for 2 hours, filtered through a crude fritted glass funnel, washed with additional 2-propanol (200 mL) and dried in a vacuum oven at 80 ° C. 140.1 g (90.4% isolated yield) of 3,3 '-(oxy-di-1,4-phenylene) -4,4'-bis [4-phenylethynylphenyl] -2,5-diphenyl Cyclopentadienone (Formula II) is obtained as a dark purple crystalline powder. HPLC analysis showed that the monomer of formula (II) was present at 98.56 area% in a balance comprising two trace byproducts.

Example 14

Differential Scanning Calorimeter of High Purity Monomer of Formula II

Differential Scanning Calorimetry (DSC) is performed using 3.6 mg of the high purity monomer of Formula II obtained in Example 13D. DSC 2910 Modular DSC (TA Instruments) is used and a heating rate of 7 ° C./min from 25 ° C. to 500 ° C. under a nitrogen flow stream of 45 cm 2 / min. The endothermic transition of the non-mainstream is minimally observed at 244.2 ° C. (18.95 joules / g) with an onset temperature of 234.6 ° C. and a termination temperature of 255.0 ° C. Immediately thereafter, a major exothermic transition occurs at 259.3 ° C. (232.4 joules / g), which may contribute to the Diels Alder reaction of the phenylethynyl and cyclopentadienone groups. The onset temperature for this exothermic transition is 255.0 ° C and the termination temperature is 352.0 ° C. Secondary scans using the conditions described above showed no glass transition temperature or any other transition. The sample recovered from the DSC analysis is a hard pale yellow fused transparent solid.

Example 15

Preparation of 4,4'-bis [(4-phenylethynylphenyl) glyoxalyl] phenyl ether with reduced palladium content and conversion to high purity monomer of formula II with reduced palladium content

The synthesis of Example 13 C is repeated, but the improved method is used for crystallization and recovery of the product as follows: 4,4′-bis [(4-bromophenyl) gly by HPLC analysis after cumulative 14.5 hours. Confirm that oxalyl] phenyl ether reactant is fully converted. At this point, the addition funnel is filled with deionized water (225 mL) while maintaining the temperature at 80 ° C. and added dropwise to the stirred solution. After the initial water addition, sodium diethyldithiocarbamate trihydrate (8.33 g, 0.037 mol) is added to the solution in the reactor. After 1.1 h at a temperature of 80 ° C., the addition funnel is filled with deionized water (225 mL) while maintaining the temperature at 80 ° C. and added dropwise to the stirred solution. After the addition of water, the heating is stopped and the stirred solution is slowly cooled and crystallized and then filtered through a coarse fritted glass funnel. The yellow powder layer packed on the filter is washed with deionized water (400 mL) and then stripped off and divided into approximately equal amounts of 8 and then in a waring blender with 400 mL of deionized water for one. The washed product is recovered by filtration with an intermediate fritted glass funnel and dried in a vacuum oven at 100 ° C. to yield 250.64 g of 4,4′-bis [(4-phenylethynylphenyl) glyoxalyl] phenyl ether. . HPLC analysis confirmed the presence of the desired product at 100 area%. Neutron radioactivity analysis of the product aliquots confirmed the presence of 70 ± 4 ppm of Pd. 106.6 g of 4,4'-bis [(4-phenylethynylphenyl) glyoxalyl] phenyl ether was dissolved in warm toluene (2800 ml), and then added to the silica gel layer using additional toluene (700 ml) as eluent. Pass it through. The evaporation from silica gel chromatography was rotary evaporated to yield 105.47 g of product, which was dissolved in N, N-dimethylformamide (1129.5 g) and charged to a 2 L three-necked round bottom reactor with magnetic stir bar. The reactor is further equipped with an addition funnel, a thermometer with a thermostatically heated heating mantle, and a chilled (2 ° C.) condenser. The addition funnel is filled with 89.1 ml of deionized water. After starting stirring and heating to 80 ° C., deionized water is added dropwise to the stirred solution while maintaining a temperature of 80 ° C. After the initial water addition, sodium diethyldithiocarbamate trihydrate (3.36 g, 0.0149 mol) is added to the solution in the reactor. After 4 hours at 80 ° C., the addition funnel is filled with deionized water (89.1 mL) while maintaining the temperature at 80 ° C. and added dropwise to the stirred solution. After the addition of the water, the heating is stopped and the stirred solution is slowly cooled, crystallized and filtered over a coarse fritted glass funnel. The yellow powder layer packed on the filter was washed with deionized water and then the moist product cake (141.1 g) was dissolved in warm toluene (2400 mL) and then passed through a layer of silica gel using additional toluene (650 mL) as eluent. . Emissions from silica gel chromatography are passed through a fresh second layer of silica gel using the method described above followed by rotary evaporation of the release from silica gel to yield 86.74 g of product. Neutron radioactivity analysis of product aliquots revealed that Pd was undetectable at the detection limit of 0.1 ppm. This product was converted to 3,3 '-(oxy-di-1,4-phenylene) -4,4'-bis [4-phenylethynylphenyl] -2,5- using the synthesis method of Example 13D. Conversion to diphenylcyclopentadienone (II) yields a high purity product with reduced palladium content.

Example 16

Preparation of 4,4'-bis [(4-phenylethynylphenyl) glyoxalyl] phenyl ether with reduced palladium content and conversion to high purity monomer of formula II with reduced palladium content using recrystallization

Toluene (798.7 g) boiling 4,4'-bis [(4-phenylethynylphenyl) glyoxalyl] phenyl ether sample (88.28 g) containing 8.5 ± 0.4 ppm Pd by neutron radiation analysis Dissolved in a mixture of 2-propanol (199.75 g) and deionized water (5.0 mL). After recrystallization of the resulting solution, the crystalline product is recovered on a coarse fritted glass funnel and dried in a vacuum oven at 80 ° C. to yield 79.7 g of pale yellow crystalline product. Neutron radioactivity analysis of product aliquots revealed that Pd was undetectable at the detection limit of 0.1 ppm. This product was converted to 3,3 '-(oxy-di-1,4-phenylene) -4,4'-bis [4-phenylethynylphenyl] -2,5- using the synthesis method of Example 13D. Conversion to diphenylcyclopentadienone (II) yields a product with reduced palladium content.

Example 17

Preparation of Monomers of Formula II with Low Metal and Ion Content

Example 13 The synthesis of D was repeated to 170 g of 3,3 '-(oxy-di-1,4-phenylene) -4,4'-bis [4-phenylethynylphenyl] -2,5-diphenyl Cyclopentadienone (II) was obtained (purity 97.2 area% by HPLC analysis). This product is passed through silica gel chromatography using an eluent consisting of 25% by volume tetrahydrofuran and 75% by volume toluene. The columns and all glassware used for chromatography are washed successively with dilute aqueous acid, electronic water and electronic 2-propanol to remove metal and ionic contaminants. The packed silica gel layer is prewashed with tetrahydrofuran. Use plastic containers and plastic tools free of metals and ionic materials. The eluate obtained by silica gel chromatography is crystallized by the addition of electronic grade 2-propanol. The resulting crystalline product was collected by filtration and dried in a vacuum oven to give 158 g (92.9% recovery) of the monomer of formula II. Trace metal analysis of the product aliquots were as follows: aluminum = 73ppb, calcium = 210ppb, chromium = 5ppb, copper = 19ppb, iron = 30ppb, lead = 2ppb, magnesium = 16ppb, manganese = 1ppb, nickel = 4ppb, potassium = 40 ppb, sodium = 300 ppb, zinc = 86 ppb, barium, beryllium, bismuth, cadmium, cesium, cobalt, gallium, indium, lithium, molybdenum, libidium, silver, strontium, thorium, tin, titanium, vanadium and zirconium are all detected Below the limit (the actual limit of quantification for all these undetected metals is below 10 ppb). Neutron radiation analysis revealed that Pd was undetectable at the detection limit of 0.1 ppm.

Example 18

Synthesis of Monomers of Formula (VII)

A. 3- Bromophenylacetyl Chloride synthesis

3-bromophenylacetic acid (28.13 g, 0.1308 mol) and N, N-dimethylformamide (0.56 mL) were added to a pre-dried 1 L glass monocylinder round bottom Schlenk reactor with magnetic stir bar pre-dried under dry nitrogen atmosphere do. The reactor is sealed under dry nitrogen and then placed on a Schlenk line under slightly positive nitrogen pressure. Thionyl chloride (207 ml) is added to a predried glass addition funnel equipped with a Schlenk adapter under a dry nitrogen atmosphere, then sealed under dry nitrogen and placed on a Schlenk line. After connecting the reactor and the addition funnel under dynamic nitrogen flow, thionyl chloride is added dropwise to the stirred reactor. While maintaining a nitrogen flow in the Schlenk reactor, gas from the reaction is introduced into the scrubbing facility through the Schlenk adapter on the addition funnel. When finished adding thionyl chloride, the addition funnel under dynamic nitrogen flow is replaced with a condenser covered with a Schlenk adapter entering the cleaning facility. The reactor contents are gently heated to 60 ° C. using a thermostatic heating mantle. After holding at 60 ° C. for 2.5 hours, excess thionyl chloride is removed from the product by applying vacuum from the Schlenk manifold until 60 ° C. and 632 millitorr are achieved. The resulting 3-bromophenylacetyl chloride product (30.55 g, 100% isolation yield) is stored under dry nitrogen until use.

B. 4,4'- Vis [(3- Bromophenyl ) Acetyl ] Synthesis of Phenyl Ether

Diphenyl ether (11.13 g, 0.06539 mol), aluminum chloride (17.79 g, 0.1334 mol) and anhydrous 1,2-dichloroethane (115 mL) were pre-dried 500 mL with magnetic stir bar pre-dried under dry nitrogen atmosphere Add to a glass three neck round bottom reactor. The reactor is sealed under dry nitrogen and then placed on a Schlenk line under slightly positive nitrogen pressure. The ice and salt baths are then placed under the reactor 22 minutes before the start of the reaction. 3-bromophenylacetyl chloride (556.26 g, 2.361 mol) obtained in A was added to a pre-dried glass addition funnel equipped with a Schlenk adapter under a dry nitrogen atmosphere, then sealed under dry nitrogen and placed on a Schlenk line. After connecting the reactor and the addition funnel under dynamic nitrogen flow, the 3-bromophenylacetyl chloride solution is added dropwise to the stirred reactor over 83 minutes. 3.8 hours after the reaction, remove the reactor from the Schlenk line and pour the contents onto crushed ice in a 4 L beaker. After the ice has melted, the precipitated product is diluted with sufficient deionized water to a volume of 1 L and then dichloromethane (1.15 L) is added. The aqueous layer is removed using a separatory funnel and the remaining dichloromethane solution is washed with deionized water (300 mL) and dried over anhydrous sodium sulfate. The resulting slurry is filtered through a medium fritted glass funnel. The filtrate was evaporated by rotary evaporation to remove the solvent, followed by further drying in a vacuum oven at 80 ° C. to obtain 39.04 g of 4,4′-bis [(3-bromophenyl) acetyl] phenyl ether (the apparent isolation yield exceeded 100%). To obtain. HPLC analysis confirmed the presence of the desired product at 76.7 area%.

C. 4,4'- Vis [(3- Bromophenyl ) Glyoxalyl ] Synthesis of Phenyl Ether

Equipped with a glass mechanical stir bar with 4,4'-bis [(3-bromophenyl) acetyl] phenyl ether (39.04 g, nominal 0.0692 mol) and dimethylsulfoxide (750 ml) obtained from B above with a teflon paddle It is added to a 2 liter glass three neck round bottom reactor. The reactor is further equipped with a condenser (not chilled), a thermometer and a thermostatically heated heating mantle entering the scrubber. Stirring and heating of the reactor contents are initiated to bring the solution to 35 ° C. Aqueous 48% hydrobromic acid (81.65 g) was added dropwise to the stirred 35 ° C. slurry in the reactor over 7 minutes to induce exotherm to 49 ° C. It is then heated to 100 ° C. over 42 minutes. After 2.9 h at a reaction temperature of 100 ° C., the hot product solution is diluted in 4 L of deionized water and then stirred as a slurry for 16 h and filtered through a coarse fritted glass funnel. The pale yellow powder layer packed on the filter was washed with deionized water and then removed and recrystallized as a moist product from boiling ethanol (cooled to room temperature and maintained for 16 hours), recovered by filtration and dried in a vacuum oven to give 30.1 g (73.5) Isolation yield in%) of 4,4'-bis [(3-bromophenyl) glyoxalyl] phenyl ether. HPLC analysis demonstrates that the desired product, with a single byproduct, is present at 98.62 area%. ¹ H NMR analysis confirms the structure of the product.

D. 4,4'- Vis [3- Phenylethynylphenyl ) Glyoxalyl ] Synthesis of Phenyl Ether

4,4'-bis [(3-bromophenyl) glyoxalyl] phenyl ether (21.56 g, 0.0364 mol) obtained in the above C, phenylacetylene (1.35 g, 0.0132 mol), triethyl sparged with dry nitrogen N, N-dimethylformamide (231 g) sparged with amine (20.11 g, 0.1987 mol), triphenylphosphine (0.48 g, 0.00183 mol), palladium (II) acetate (0.07 g, 0.00031 mol), and dry nitrogen Is added to a pre-dried 2 liter glass three-neck round bottom reactor with a magnetic stir bar pre-dried under a dry nitrogen atmosphere. The reactor is further equipped with a thermometer with a fan cooled spiral condenser, an addition funnel, and a thermostatically heated heating mantle. Additional phenylacetylene (7.64 g, 0.0748 mol) is added to the addition funnel. 30 minutes after the start of stirring and heating is reached, the dropwise addition of phenylacetylene is started and completed after 20 minutes. HPLC analysis after cumulative 20.7 hours confirms that the 4,4'-bis [(3-bromophenyl) glyoxalyl] phenyl ether reactant was completely converted and no monobromonophenylethynyl intermediate was detected. Pour the reactor contents onto crushed ice in a 4 L beaker. After the ice has melted, the precipitated product is recovered by filtration through an intermediate fritted glass funnel. The product cake on the funnel is washed twice with 200 ml of deionized water and then directly recrystallized as a moist product from boiling acetonitrile. The recrystallization solution was cooled to room temperature and held for 16 hours to give 13.87 g (60% isolated yield) of 4,4'-bis [3-phenylethynylphenyl) glyoxalyl] phenyl ether as light tan crystalline product. To obtain. HPLC analysis demonstrates the presence of 98.43 area% of the desired product with a single byproduct. ¹ H NMR analysis and EI MS analysis confirm the structure of the product.

E. 3,3 '-(oxy-di-1,4-phenylene) -4,4'-bis [3-phenylethynylphenyl] -2,5-diphenylcyclopentadienone Synthesis of Formula (VII)

4,4'-bis [(3-phenylethynylphenyl) glyoxalyl] phenyl ether (13.29 g, 0.0209 mol), 1,3-diphenylacetone (9.91 g, 0.0471 mol) obtained in the above D, 2 Propanol (177 mL) and toluene (133 mL) are added to a 2 L four neck round bottom reactor. The reactor was agitated with a chilled (2 ° C.) condenser, a thermometer with a thermostatically heated heating mantle, a Cryzen adapter with an addition funnel and nitrogen sparge tube, and a Teflon blade stirrer coupled to a variable speed motor to provide mechanical agitation. It has an additional shaft. The addition funnel was heated with 1M tetrabutylammonium hydroxide (1.11 mL) in methanol dissolved in 2-propanol (22 mL) under a dry nitrogen atmosphere, and when the stirred solution reached 80 ° C., the sparging tube was removed and nitrogen was Replace with an overhead inlet for The solution in the addition funnel starts to add to the reflux stirred slurry and completes over 10 minutes, during which the yellow solution turns into a deep reddish purple solution. 15 minutes after addition of the catalyst solution, the deep reddish purple solution becomes cloudy. At this point, HPLC analysis reveals the complete conversion of the 4,4'-bis [(3-phenylethynylphenyl) glyoxalyl] phenyl ether reactant with the optimal formation of the desired product and the formation of minimal byproducts. After an additional 8 minutes, heating is stopped and the heating mantle is removed from the reactor, additional 2-propanol (400 mL) is added to the reactor and the reaction mixture is cooled to room temperature using a cooling fan outside the reactor. When the stirred slurry reaches 25 ° C., the product is recovered by filtration through a coarse fritted glass funnel. The crystalline product on the funnel is washed with 100 ml of 2-propanol and then dropped back into the reactor washed with 2-propanol. Additional 2-propanol (400 mL) was added to the reactor, stirred for 15 minutes, filtered through a coarse fritted glass funnel, washed with additional 2-propanol (50 mL) and dried in a vacuum oven at 80 ° C. 20.12 g (97.7% isolation yield) of 3,3 '-(oxy-di-1,4-phenylene) -4,4'-bis [3-phenylethynylphenyl] -2,5-diphenylcyclo Pentadienone is obtained as a purple crystalline powder. HPLC analysis confirmed the presence of 96.3 area% of monomers of formula (VIII) containing a single trace by-product.

Example 19

Differential Scanning Calorimeter of Monomers of Formula (VII)

Differential Scanning Calorimetry (DSC) is performed using 3.8 mg of the monomer of Formula (VII) obtained in Example 18E above. DSC 2910 Modular DSC (TA Instruments) is used and a heating rate of 7 ° C./min from 25 ° C. to 500 ° C. under a nitrogen flow stream of 45 cm 2 / min. Non-mainstream endothermic transitions are minimally observed at 195.3 ° C. (20.8 joules / g) with an onset temperature of 189.1 ° C. and a termination temperature of 222.1 ° C. Immediately thereafter, a major exothermic transition occurs at 249.4 ° C. (243.4 joules / g), which may contribute to the Diels Alder reaction of the phenylethynyl and cyclopentadienone groups. The onset temperature of this exothermic transition is 222.1 ° C and the termination temperature is 329.0 ° C. Secondary scans using the conditions described above showed no glass transition temperature or any other transition. The sample recovered from the DSC analysis is a hard pale yellow fused transparent solid.

Example 20

Preparation of Porous Matrix from Monomer and Star Polymer of Formula (II)

A. Responsive Preparation of Star Polymer

A 2.5 L glass polymerization reactor, washed with hot cyclohexane and vacuum dried, is charged with 2 L cyclohexane. The reactor is heated to 50 ° C. and 25.2 ml (10.86 mmol) of 0.43 M secondary-BuLi, 49.74 g of styrene, followed by 74 ml of THF. The dark orange solution is stirred for 15 minutes. The polymer is taken (Sample A) and 5.39 g (41.41 mmol, 3.8 equiv) of para-divinylbenzene contained in cyclohexane are added to give a very dark red solution. After 30 minutes, 47.5 g of styrene are added to give a dark orange solution. After 15 minutes, the reaction is taken (Sample B) and 4.8 g of ethylene oxide is added to give a colorless viscous solution. After 1 hour, 5.44 g (22.60 mmol, 2.1 equiv) of 4- (phenylethynyl) benzoyl chloride contained in tetrahydrofuran are added. After an additional hour, the reactor is cooled down and the contents taken out. An aliquot of the final star polymer (Sample C) is isolated by precipitation in MeOH. The results of GPC analysis of the samples are as follows (data are relative to polystyrene standards except for absolute values):

Ultraviolet analysis shows that the star polymer contains on average 2.25% by weight of diphenylacetylene, or 22.6 units of diphenylacetylene per star polymer.

B. Formula II Monomers Having Responsive B-step of the star polymer

To Schlenk tube is added 1.2857 g of the reactive polystyrene star polymer obtained in A above (absolute value Mn = 241,000, absolute Mw = 345,000, average number of diphenylacetylene residues per star polymer = 23) and gamma-butyrolactone (8.75 g) do. The tube is connected to a static nitrogen source and immersed in an oil bath heated to 45 ° C. The mixture is stirred overnight. Subsequently, monomer II (3.00 g) is added to the tube. The mixture is stirred and degassed by applying several vacuum / nitrogen cycles. After leaving the tube under static nitrogen pressure, the oil bath is heated to 200 ° C. and maintained for 8.5 hours. Remove the tube from the oil bath and allow it to cool. Dilute the mixture with cyclohexanone (8.3928 g). Analysis of the mixture by gel permeation chromatography showed Mn = 3545 and Mw = 35,274 for polystyrene criteria.

C. Monomer II and Responsive Porous from star polymer Matrix Produce

The mixture obtained in B was spin-coated onto a 4 "silicon wafer, the hot plate was baked at 150 ° C. for 2 minutes to remove the solvent, then heated to 430 ° C. at 7 ° C./min and 430 minutes in a nitrogen purged oven. The resulting porous film has a refractive index of 1.47 (comparable to 1.64 for a fully densified polymer) and a dielectric constant of 2.13.

Example 21

Preparation of Porous Matrix from Monomer and Higher Branched Polymers of Formula (II)

A. Preparation of Reactive Higher Branched Polyester

To 3.11 g of Bolton H40 (commercially available from Perstorp Corp.) (0.439 mmol; 28.03 mmol -OH) in 40 ml of THF stirred at room temperature for 15 minutes, 1.18 ml (0.860 g; 8.5 mmol) of Et ₃ N is added. . After the mixture was stirred for 15 minutes, 2.03 g (8.41 mmol) of 4- (phenylethynyl) benzoyl chloride was added dropwise as a solution in 40 mL THF. The mixture is stirred overnight at room temperature. To the reaction mixture is then added 3.90 mL (28 mmol) of Et ₃ N followed by 3.31 g (54 mmol; 2.7 mL) of benzoyl chloride. The mixture is stirred at rt overnight then gently heated to reflux for 4-6 h. The reaction mixture is added to ˜200 g ice and 10 mL concentrated HCl with vigorous stirring. After 30 minutes the reaction mixture is taken up in 200 mL of CHCl ₃ and transferred to a separatory funnel to remove the aqueous layer and the organic layer is washed with 10% HCl ( ₂ × 100 mL), H ₂ O ( ₂ × 100 mL) and 5% NaHCO ₃ (1 × 100 mL). . The mixture is dried over MgSO ₄ . The mixture is filtered and concentrated to give a viscous liquid. The viscous liquid is devolatilized by Kugelrohr distillation under complete vacuum (Tmax = 140 ° C.). The weight of the glassy product is 4.61 g; Theory 6.87 g; Yield = 67%.

B. B-Step of Reactive Higher Branched Polymer Using Monomers of Formula (II)

To the Schlenk tube is added the reactive higher branched polyester obtained in A above (bolton H-40 functionalized with 19.2 phenylethynylbenzoate group and 44.8 benzoate group) and gamma-butyrolactone (8.75 g). . The tube is connected to a fixed nitrogen source and immersed in an oil bath heated to 45 ° C. The mixture is stirred overnight. Subsequently, monomer II (3.00 g) is added to the tube. The mixture is stirred and degassed by applying several vacuum / nitrogen cycles. After leaving the tube under fixed nitrogen pressure, the oil bath is heated to 200 ° C. and maintained for 8.5 hours. Remove the tube from the oil bath and allow it to cool. The mixture is diluted with cyclohexanone (6.25 g). Analysis of the mixture by gel permeation chromatography showed Mn = 4001 and Mw = 23,838 for polystyrene criteria.

C. Monomer Porosity from II and reactive branched polymers Matrix Produce

The mixture obtained in B was spin-coated onto a 4 "silicon wafer, the hot plate was baked at 150 ° C. for 2 minutes to remove the solvent, then heated to 430 ° C. at 7 ° C./min and 430 minutes in a nitrogen purged oven. Keep at C. The resulting porous film has a refractive index of 1.59 (comparable to 1.64 for a fully densified polymer).

Example 22

Synthesis of Monomers of Formula XII

A. 3,5- Dibromophenylacetic acid Conversion to Potassium Salt

Commercial 3,5-dibromophenylacetic acid (292.95 g, 1.0 mol) (99.5 area% by HPLC analysis) was added to a magnetically stirred solution of nominal 85% potassium hydroxide (69.3 g) in deionized water (3.0 L) Then heat. At 51 ° C. a solution is formed and the heating is stopped. The solution was rotary evaporated in vacuo to give a slightly moist white solid product (360.2 g) which was recovered and extracted twice with dichloromethane (500 mL). The extracted powder product contained in the monocyte round bottom glass flask is sealed using a Schlenk adapter which induces a vacuum. The flask is further heated to 40 ° C. using a thermostatic heating mantle and held on a vacuum line until a vacuum of 400 millitorr is reached. The recovered weight of potassium 3,5-dibromophenylacetate thus prepared is 332.3 g (containing excess potassium hydroxide residue).

B. 3,5- Dibromophenylacetyl Chloride synthesis

The potassium 3,5-dibromophenylacetate product (332.3 g, 1.0 mol nominal) and anhydrous dichloromethane (2.0 L) obtained in A were added to a 5 L glass three-neck round bottom reactor pre-dried under a dry nitrogen atmosphere. The reactor is sealed under dry nitrogen and then placed on a Schlenk line under slightly positive nitrogen pressure. Thionyl chloride (633.0 g, 5.32 mol) is added to a predried glass addition funnel equipped with a Schlenk adapter under a dry nitrogen atmosphere, then sealed under dry nitrogen and placed on a Schlenk line. The reactor and the addition funnel are combined under dynamic nitrogen flow. The dynamic nitrogen flow is maintained through the Schlenk adapter on the addition funnel so that the gas generated in the reaction is removed into the scrubbing system through the Schlenk adapter on the reactor. Mechanical agitation of the reactor contents (glass stirrer shaft with Teflon paddle) is initiated to produce a stirred slurry, to which thionyl chloride is added dropwise over 64 minutes. Three minutes after the thionyl chloride addition is complete, anhydrous N, N-dimethylformamide (2.9 g) is poured into the stirred slurry. After a further 2 hours of stirring, vacuum is applied while stopping the flow of nitrogen into the reactor. Heating is started gently using a thermostatic heating mantle with the surface temperature set at 75 ° C. Solid product remains in the reactor and the excess thionyl chloride is evaporated. At this point the heating is stopped and the vacuum is replaced by a nitrogen pad maintained under slightly positive pressure. The reactor is then sealed under nitrogen and placed in a dry nitrogen glove box. The reactor is heated back to 30 ° C. using a thermostatically heated heating mantle in a glove box and maintained in a vacuum line until a vacuum of 330 millitorr is reached. The powder product recovered from the reactor is extracted three times (500, 300 and 300 ml, respectively) successively with anhydrous diethyl ether (obtained by column chromatography drying over activated alumina under a dry nitrogen atmosphere). Each diethylether extract is decanted through a predried middle fritted glass funnel and the combined diethylether extracts are then added to a predried 2 liter glass three neck round bottom reactor with a predried magnetic stir bar. The stirred reactor was heated to 30 ° C. using a thermostatic heating mantle while applying vacuum to evaporate the diethyl ether solvent. Once the visually observed diethyl ether has evaporated, the product is held on a vacuum line for 6 hours at a vacuum in the range of 560-670 millitorr. The resulting 3,5-dibromophenylacetyl chloride product (304.7 g, 97.5% isolation yield) is recovered as off-white crystalline powder and stored under dry nitrogen until use.

A 3,5-dibromophenylacetyl chloride sample (0.1 g) is added to a pre-dried glass vial containing anhydrous methanol (1 mL) under nitrogen atmosphere. Boil the solution to remove methanol. The remaining residue is dissolved in acetonitrile and analyzed by HPLC to identify 100 area% of methyl ester product.

Differential Scanning Calorimetry (DSC) is performed using 12.2 mg of 3,5-dibromophenylacetyl chloride sealed in an aluminum pan in a dry nitrogen glove box. A DSC 2910 Modular DSC (TA Instruments) and use a heating rate of 7 ° C./min from 0 ° C. to 100 ° C. under a nitrogen flow stream of 45 cm 2 / min. For the melting of the product a single endothermic transition is observed at 51.4 ° C. minimum and enthalpy is 75.56 joules / g.

C. 4,4'- Vis [(3,5- Dibromophenyl ) Acetyl ] Synthesis of Phenyl Ether

Anhydrous 1,2-dichloroethane (557 ml), aluminum chloride (66.32 g, 0.4974 mol), followed by diphenyl ether (41.09 g, 0.2414 mol) was pre-dried 2 L with magnetic stir bar pre-dried under dry nitrogen atmosphere Add to a glass three neck round bottom reactor. The reactor is sealed under dry nitrogen and then placed on a Schlenk line under slightly positive nitrogen pressure. Agitation of the reactor contents is initiated to produce a slurry. Place an ice and salt (NaCl) bath under the reactor 20 minutes before starting the reaction. 3,5-dibromophenylacetyl chloride (152.36 g, 0.4876 mol) obtained in the above B was dissolved in anhydrous 1,2-dichloroethane (517 mL) and the resulting solution was added to the glass, which was pre-dried under a dry nitrogen atmosphere. Add to funnel. The addition funnel is equipped with a Schlenk adapter, sealed under dry nitrogen and placed on the Schlenk line. By connecting the reactor and the addition funnel under dynamic nitrogen flow and maintaining the nitrogen flow through the Schlenk adapter on the addition funnel, the gases resulting from the reaction are continuously removed into the cleaning system through the Schlenk adapter on the reactor. The 3,5-dibromophenylacetyl chloride solution is added dropwise to the stirred reactor over 168 minutes. During this time, replenish the ice and salt bath when fusion occurs. 56 minutes after the reaction, the reactor is removed from the Schlenk line and the contents are poured into a pair of 4 L beakers containing 1.5 L of magnetically stirred deionized water, each preheated to 40 ° C. The contents of the beaker are exothermic to 60 ° C. and further heated until they reach 90 ° C. and then maintained until 1,2-dichloroethane has evaporated. The slurry of coarse white powder produced in each beaker is further vacuum filtered through a coarse fritted glass funnel immediately after dilution in 1 liter of deionized water. The powder cake packed on a fritted glass funnel was washed with sufficient deionized water and then dried in a vacuum oven at 80 ° C. to 176.87 g (100% isolation yield) of 4,4′-bis [(3,5-dibromo). Phenyl) acetyl] phenyl ether is obtained. HPLC analysis confirmed the presence of the desired product at 96.02 area%.

D. 4,4'- Vis [(3,5- Dibromophenyl ) Glyoxalyl ] Synthesis of Phenyl Ether

Glass machine stirring bar with 4,4'-bis [(3,5-dibromophenyl) acetyl] phenyl ether (175.95 g, 0.2437 mol) and dimethylsulfoxide (3.62 L) obtained in C above To a 5-liter glass three-neck round bottom reactor with. The reactor is further equipped with a cryzen adapter, an addition funnel, a condenser (not chilled) entering the cleaning system, and a thermometer. Aqueous 48% hydrobromic acid (287.6 g) was added dropwise to the stirred 25 ° C. slurry in the reactor over 31 minutes to induce exotherm to 33.5 ° C. The thermostatic heating mantle is then placed on the reactor and heated gently to 100 ° C. over 107 minutes to yield a bright orange solution (“heating mildly” periodically stops heating to observe exothermic and equilibrate). State). After 2 hours at a reaction temperature of 100 ° C., HPLC analysis confirmed that the reaction was complete. The hot product solution is diluted in four 4 L beakers each containing 2.0 L of magnetically stirred deionized water. The resulting stirred product slurry is maintained for 16 hours and then vacuum filtered through an intermediate fritted glass funnel. The pale yellow powder layer packed on the filter was washed with deionized water, then removed and dried in a vacuum oven to yield 175.6 g (96.1% isolation yield) of 4,4'-bis [(3,5-dibromophenyl) Glyoxalyl] phenyl ether is obtained. HPLC analysis demonstrates the presence of 97.0 area% of the desired product in a balance including a single trace by-product. EI MS analysis confirms the structure of the product: Intact molecular ions are not observed because internal bonds are easily cleaved upon electron ionization. The group of ions concentrated at m / z 487 and m / z 263 clearly reflects the isotope pattern of the two bromine atoms for fragment ions of formula C ₂₁ H ₁₁ O ₄ Br ₂ and formula C ₇ H ₃ OBr ₂ , respectively. . These fragments result from cleavage within one glyoxalyl group. The group of ions concentrated at m / z 235 is derived from dibromophenyl ions. Ions of m / z 196 and m / z 139 (without bromine) arise from the center of the molecule. Chemical ionization (CI) is performed to observe intact molecules for molecular ion identification (using isobutane as the CI reagent gas). In the positive CI mass spectrum, the quantized group of molecular ions can be seen around 751 amu and have the isotope pattern expected in compounds containing four bromine atoms.

E. 4,4'- Vis [(3,5- Vis ( Phenylethynyl Phenyl) Glyoxalyl ] Synthesis of Phenyl Ether

4,4'-bis [(3,5-dibromophenyl) glyoxalyl] phenyl ether (175.0 g, 0.2333 mol) obtained in the above D, N, N-dimethylformamide sprayed with dry nitrogen (3064 g ), Triethylamine (257.8 g, 2.548 mol) sparged with dry nitrogen, phenylacetylene (17.3 g, 0.1694 mol), triphenylphosphine (6.19 g, 0.0236 mol) and palladium (II) acetate (0.86 g, 0.0038) mol) is added to a 5 L glass three-neck round bottom reactor with a glass mechanical stir bar with Teflon paddles. The reactor is further equipped with a thermometer with a Cryzen adapter, a fan cooled spiral condenser, an addition funnel, and a thermostatically heated heating mantle. Additional phenylacetylene (97.9 g, 0.9585 mol) is added to the addition funnel. The temperature of 80 ° C. is reached 59 minutes after stirring and heating is started. Phenylacetylene is added dropwise to the stirred solution and is completed after 114 minutes while maintaining the temperature between 79 ° C and 81 ° C. HPLC analysis after an additional 24 hours at 80 ° C. confirmed that the 4,4′-bis [(3,5-dibromophenyl) glyoxalyl] phenyl ether reactant was completely converted.

F. 4,4'- Vis [(3,5- Vis ( Phenylethynyl Phenyl) Glyoxalyl ] From phenyl ether reaction product Palladium remove

The addition funnel previously used for phenylacetylene addition was filled with deionized water (127 mL) and added dropwise to the stirred solution of E while maintaining the temperature at 80 ° C. Seven minutes after the initial water addition, sodium diethyldithiocarbamate trihydrate (9.65 g, 0.0428 mol) is added to the solution in the reactor. After 90 minutes at a temperature of 80 ° C., the addition funnel is filled with deionized water (477 mL) while maintaining the temperature at 80 ° C. and added dropwise to the stirred solution. After the addition of the water, the heating is stopped and the stirred solution is slowly cooled and crystallized over 16 hours and then vacuum filtered with an intermediate fritted glass funnel. Keep the packed yellow powder layer on the strainer until the filtrate droplets are no longer observed. The moist product cake (303.2 g) is removed from the filter and filled into a 5 L glass three-neck round bottom reactor with a glass mechanical stir bar with Teflon paddles. Then toluene is added to the reactor (1093 mL). The reactor is further equipped with a thermometer with a chilled (2 ° C.) condenser and a thermostatically heated heating mantle. After starting stirring and heating to 85 ° C., deionized water (1093 mL) is added to the reactor as a stream and then reheated to 85 ° C. After 1 hour at 85 ° C. (refluxed to warm), heating and stirring are stopped and the reactor contents are transferred to a separating funnel. After the aqueous layer is removed and decanted, the toluene solution is added back to the reactor, heated to 85 ° C. with stirring and second deionized water (1093 mL) is added. After 1 hour at 85 ° C., heating and stirring are stopped and the reactor contents are transferred to a separating funnel. After the aqueous layer is removed and decanted, the toluene solution is added back to the reactor and heated again while stirring. After 3 minutes, 2-propanol (1093 mL) is added to the stirred solution as a stream. The addition of 2-propanol brings the solution to 40 ° C. and stops stirring and heating (reactor is kept in the heating mantle to allow it to cool slowly). After 115 minutes when the temperature drops to 36 ° C., first crystals of the product form. After a further 16 hours, the crystalline product is recovered by vacuum filtration on an intermediate fritted glass funnel. The recovered product on the funnel is compressed into a tightly packed cake and then washed twice in succession with 2-propanol (150 mL) on a filter. 132.61 g (68.9% isolated yield) of 4,4'-bis [(3,5-bis (phenylethynyl) phenyl) glyoxalyl] phenyl ether after drying in a vacuum oven at 35 ° C. was obtained by crystalline pale yellow powder. Recover as. HPLC analysis confirmed the presence of the desired product at 100 area%. Neutron radioactivity analysis of the product aliquots revealed the presence of 3.5 +/- 0.3 ppm of Pd.

G. 3,3 '-(oxy-di- 1,4-phenylene) -4,4'-bis [3,5-bis (phenylethynyl ) phenyl] bis (2,5-di with low palladium content Synthesis of Phenylcyclopentadienone (Formula XII)

4,4'-bis [(3,5-bis (phenylethynyl) phenyl) glyoxalyl] phenyl ether (128.29 g, 0.1555 mol) obtained in the above F, 1,3-diphenylacetone (68.69 g, 0.3267 mol), 2-propanol (1971 mL) and toluene (659 mL) are added to a 5 liter three neck round bottom reactor. The reactor was a glass stirring chef with a chilled (2 ° C.) condenser, a thermometer with a thermostatic heating mantle, a cryzen adapter, an addition funnel, a nitrogen sparge tube, and a Teflon blade stirrer coupled to a variable speed motor to provide mechanical agitation. I am equipped with a hat. The addition funnel is charged with 1M tetrabutylammonium hydroxide (10.4 mL) in methanol dissolved in 2-propanol (204 mL) under a dry nitrogen atmosphere. Stirring, sparging with nitrogen (1.0 L / min) and heating are started and at 76 ° C. the stirred slurry is completely in solution. Once at 82 ° C., mild reflux is observed and the sparging tube is removed and replaced with an overhead inlet for nitrogen. The solution in the addition funnel begins to add to the reflux stirred slurry and is completed over 12 minutes, during which the yellow solution turns to a deep red solution. After addition, the dark red solution turns into a thin granular slurry and after a further 3 minutes into a thick granular slurry. After another 4 minutes, the heating was stopped and the heating mantle was removed from the reactor and HPLC analysis showed complete conversion of the 4,4'-bis [(3,5-bis (phenylethynyl) phenyl) glyoxalyl] phenyl ether reactant and At the same time the optimal formation of the desired product and the formation of minimal byproducts are confirmed. After another 11 minutes, further 2-propanol (1971 L) is added to the reactor and the reaction mixture is cooled to 25 ° C. using a cooling fan outside the reactor. When the stirred slurry reaches 25 ° C., the product is recovered by filtration through an intermediate fritted glass funnel. The crystalline product is compressed into a packed cake and then washed with additional 2-propanol on the funnel until the filtrate becomes clear. 176.77 g (96.9% isolation yield) of 3,3 '-(oxy-di-1,4-phenylene) -4,4'-bis [3,5 by drying in a vacuum oven at 30 ° C. for 72 hours. -Bis (phenylethynyl) phenyl] bis (2,5-diphenylcyclopentadienone) is recovered as a purple crystalline powder. HPLC analysis confirmed the presence of 96.3 area% of the desired monomer (Formula XII) in a balance comprising a single trace byproduct. Neutron radioactivity analysis of the product aliquots revealed no Pd at the detection limit of +/- 0.2 ppm.

Example 23

Differential Scanning Calorimeter of Monomers of Formula XII

Differential Scanning Calorimetry (DSC) is performed using 2.9 mg of the monomer of Formula XII obtained in Example 22G. DSC 2910 Modular DSC (TA Instruments) is used and a heating rate of 7 ° C./min from 25 ° C. to 500 ° C. under a nitrogen flow stream of 45 cm 2 / min. Exothermic transitions that may contribute to the Diels-Alder reaction of the phenylethynyl and cyclopentadienone groups are observed at 303.0 ° C. (178.1 joules / g) at maximum. The onset temperature of this abrupt exothermic transition is 292.1 ° C. and the termination temperature is 347.5 ° C. The second exothermic transition, which may contribute to the reaction of the phenylethynyl group, is maximally observed at 424.5 ° C. (46.2 joules / g). The onset temperature for this wide and flat exothermic transition is 390.1 ° C and the termination temperature is 484.8 ° C. Secondary scans using the conditions described above showed no glass transition temperature or any other transition. The sample recovered from the DSC analysis is a hard light amber fused transparent solid.

Example 24

Synthesis of Monomers of Formula (XXV)

A. 1,3- Vis [(4- Bromophenyl ) Acetyl ] -5- Bromobenzene synthesis

Bromobenzene (157.0 g, 1.0 mol) and 5-bromo-1,3-phenylenediacetyl chloride (17.43 g, 0.0562 mol, 0.1124-COCl equiv) were preliminary with a magnetic stir bar dried under a dry nitrogen atmosphere It is added to a dried 500 ml glass monocyte round bottom reactor. While maintaining a dry nitrogen atmosphere, the reactor contents are stirred to produce a cloudy amber solution. Aluminum chloride (18.0 g, 0.1350 mol) is added to the reactor in aliquots of 0.50 g every 3 minutes. Three minutes after the addition of aluminum chloride (total addition time is 105 minutes), a dark amber solution containing floating white particles is taken for HPLC analysis. HPLC analysis confirmed that 5-bromo-1,3-phenylenediacetyl chloride was completely converted to the desired product. After an additional 57 minutes, the reactor is removed from the nitrogen atmosphere and the contents poured into a 4 l beaker containing approximately 1000 g of ice, followed by the addition of deionized water to a total volume of approximately 2 l. After the ice melts, methylene chloride (1 L) is added to the resulting mixture, which is then shaken and placed in a separating funnel to mix the aqueous and organic phases. Once the aqueous layer is dissolved, pour out and the remaining solution in the separatory funnel is washed with deionized water (500 ml). The washed solution is dried over anhydrous sodium sulfate and vacuum filtered through an intermediate fritted glass funnel. Rotary evaporation of the filtrate affords 30.42 g of a powder containing 88.7 area% of the desired product. 25.03 g (80.8% isolation yield) of bright golden 1,3-bis [(4-bro), recrystallized from boiling acetonitrile (200 ml used, the boiling solution was cooled slowly to room temperature and then cooled to 4 ° C). Mophenyl) acetyl] -5-bromobenzene is obtained. HPLC analysis confirmed the presence of the desired product at 97.7 area%.

B. 1,3- Vis [(4- Bromophenyl ) Glyoxalyl ] -5- Bromobenzene synthesis

Glass having 1,3-bis [(4-bromophenyl) acetyl] -5-bromobenzene (35.72 g, 0.0648 mol) and dimethylsulfoxide (1 L) prepared using the method of A above with a Teflon paddle Add to a 2 L glass three neck round bottom reactor with mechanical stir bar. The reactor is further equipped with a cryzen adapter, an addition funnel, a condenser (not chilled) and a thermometer entering the cleaning system. Aqueous 48% hydrobromic acid (76.5 g) was added dropwise to the stirred 22 ° C. slurry in the reactor over 27 minutes to induce exotherm to 30.5 ° C. The thermostatic heating mantle is then placed on the reactor and gently heated to 100 ° C. over 87 minutes to yield an amber solution (“heating mildly” periodically stops heating to observe exothermic and equilibrium conditions). To mean). HPLC analysis after 190 minutes at a reaction temperature of 100 ° C. confirms that the reaction is complete. The hot product solution is diluted in three 4 L beakers each containing 2 L of magnetically stirred deionized water. The resulting stirred product slurry is maintained for 16 hours and then vacuum filtered through an intermediate fritted glass funnel. The pale yellow powder layer packed on the filter was washed with deionized water, then removed and dried in a vacuum oven at 60 ° C. to 36.83 g (98.1% isolation yield) of 1,3-bis [(4-bromophenyl) gly Oxalyl] -5-bromobenzene is obtained. HPLC analysis revealed that the desired product was present at 100.0 area%. EI MS analysis confirms the structure of the product: Intact molecular ions are not observed (groups around m / z 578) because internal bonds are readily cleaved upon electron ionization. The group of ions around m / z 395 and m / z 183 clearly reflects the presence of bromine for fragment ions of formula C ₁₅ H ₇ O ₃ Br ₂ and formula C ₇ H ₄ OBr, respectively. These fragments result from cleavage within one glyoxalyl group. The ion pair of m / z 155 is derived from bromophenyl ions. Molecular isotope patterns from the EI MS spectrum are in good agreement when compared to the expected theoretical formula. Chemical ionization (CI) is performed to better observe the intact molecule for molecular ion identification (using isobutane as the CI reagent gas). In the positive CI mass spectrum, the quantized group of molecular ions can be seen around 579 amu and have the isotopic pattern expected for compounds containing three bromine atoms.

C. 1,3- Vis [(4- Phenylethynylphenyl ) Glyoxalyl ] -5- Of phenylethynylbenzene synthesis

1,3-bis [(4-bromophenyl) glyoxalyl] -5-bromobenzene (36.68 g, 0.0634 mol) obtained in the above B, N, N-dimethylformamide sprayed with dry nitrogen (650 g ), Triethylamine (52.5 g, 0.519 mol) sparged with dry nitrogen, phenylacetylene (3.52 g, 0.0345 mol), triphenylphosphine (1.26 g, 0.0048 mol) and palladium (II) acetate (0.174 g, 0.000775) mol) is added to a pre-dried 1 L glass three-neck round bottom reactor with a glass mechanical stir bar with Teflon paddles. The reactor is further equipped with a thermometer with a Cryzen adapter, a fan cooled spiral condenser, an addition funnel, and a thermostatically heated heating mantle. Additional phenylacetylene (19.94 g, 0.1952 mol) is added to the addition funnel. After 80 minutes of stirring and heating is started, a temperature of 80 ° C. is reached. Phenylacetylene is added dropwise to the stirred solution and is completed after 43 minutes while maintaining the temperature between 79 ° C and 81 ° C. HPLC analysis after an additional 17 hours at 80 ° C. confirms that the 1,3-bis [(4-bromophenyl) glyoxalyl] -5-bromobenzene reaction was completely converted. The resulting product is poured into two 4 L beakers each containing 2.5 L of self-stirred deionized water. The stirred product slurry obtained is maintained for 3 hours and then vacuum filtered through a coarse fritted glass funnel. After washing the layer of pale yellow powder packed on the filter with deionized water, it is removed as a moist product cake (115.9 g) and magnetically stirred as a slurry for 1 hour in a beaker containing 1.5 L of boiling acetone. After cooling to room temperature the product was recovered by vacuum filtration on a coarse fritted glass funnel and dried in a vacuum oven at 25 ° C. in 33.52 g (82.3% isolated yield) of 1,3-bis [(4-phenylethynylphenyl ) Glyoxalyl] -5-phenylethynylbenzene. HPLC analysis revealed that the desired product was present at 99.4 area%.

D. 3,3 '-(1,3-phenylene-5-phenylethynyl) -4,4'-bis [(4-phenylethynylphenyl] bis (2,5-diphenylcyclopentadienone (Formula XX Ⅴ ) Synthesis

1,3-bis [(4-phenylethynylphenyl) glyoxalyl] -5-phenylethynylbenzene (17.37 g, 0.0270 mol) obtained in the above C, 1,3-diphenylacetone (12.79 g, 0.0608 mol), 2-propanol (229 mL) and toluene (171 mL) are added to a 1 L three-neck round bottom reactor. The reactor was a glass stirring chef with a chilled (2 ° C.) condenser, a thermometer with a thermostatic heating mantle, a cryzen adapter, an addition funnel, a nitrogen sparge tube, and a Teflon blade stirrer coupled to a variable speed motor to provide mechanical agitation. I am equipped with a hat. The addition funnel is charged with 1M tetrabutylammonium hydroxide (1.78 mL) in methanol dissolved in 2-propanol (7 mL) under a dry nitrogen atmosphere. Stirring, nitrogen sparging (1.0 l / min) and heating are started. Once 80 ° C. is reached, mild reflux is observed and the sparging tube removed and replaced with an overhead inlet for nitrogen. The solution in the addition funnel begins to add to the reflux stirred slurry and completes over 15 minutes during which the yellow slurry turns to a deep red solution. After 35 minutes at 80 ° C., a further catalyst solution prepared by diluting 1M tetrabutylammonium hydroxide (0.45 ml) in methanol in 2-propanol (1.8 ml) under dry nitrogen atmosphere is injected into the solution. After an additional 30 minutes at 80 ° C., the dark red solution becomes a thick granular slurry and samples for HPLC analysis. After an additional 18 minutes, the heating was stopped and the heating mantle was removed from the reactor and HPLC analysis showed that the 1,3-bis [(4-phenylethynylphenyl) glyoxalyl] -5-phenylethynylbenzene reactant was completely converted to the desired target. Ensure optimal formation of products and formation of minimal byproducts. Further 2-propanol (229 mL) is added to the reactor and the reaction mixture is cooled to 25 ° C. using a cooling fan outside the reactor. When the stirred slurry reaches 25 ° C., the product is recovered by filtration through an intermediate fritted glass funnel. The crystalline product is compressed into a packed cake and then washed with additional 2-propanol on the funnel until the filtrate becomes clear. The product on the funnel is recovered and placed in a transparent reactor containing fresh 2-propanol (500 mL), then stirred quickly for 30 minutes, recovered on a crude fritted glass funnel and washed with additional 2-propanol to give a clear filtrate. Dried in a vacuum oven at 25 ° C. for 3 days to give 24.28 g (90.6% isolation yield) of 3,3 '-(1,3-phenylene-5-phenylethynyl) -4,4'-bis [(4 -Phenylethynylphenyl] bis (2,5-diphenylcyclopentadienone is recovered as a reddish purple crystalline powder. Balance comprising two single trace by-products (0.6 and 1.4 area% respectively) by HPLC analysis 98.0 area% of the desired monomer (formula XXV) is confirmed to exist.

Example 25

Differential Scanning Calorimeter of Monomers of Formula (XXV)

Differential Scanning Calorimetry (DSC) is performed using 2.5 mg of the monomer of Formula XXV obtained in Example 24D. DSC 2910 Modular DSC (TA Instruments) is used and a heating rate of 7 ° C./min from 25 ° C. to 500 ° C. under a nitrogen flow stream of 45 cm 2 / min. Exothermic transitions that may contribute to the Diels-Alder reaction of the phenylethynyl and cyclopentadienone groups are observed at 242.7 ° C. (120.3 joules / g) at maximum. The onset temperature for this abrupt exothermic transition is 239 ° C and the termination temperature is 322.5 ° C. The onset temperature is somewhat merged with some (approximately enthalpy = 3joules / g) endothermic dissolution transition minimum at 237.7 ° C. The second exothermic transition, which may contribute to the reaction of the phenylethynyl group, is maximally observed at 453.7 ° C. (42.8 joules / g). The onset temperature for this wide and flat exothermic transition is 375.6 ° C. and the termination temperature is 497.7 ° C. Secondary scans using the conditions described above showed no glass transition temperature or any other transition. The sample recovered from the DSC analysis is a hard light amber fused transparent solid.

Example 26

Palladium content low 3,3 '-(oxy-di-1,4-phenylene) -4,4'-bis [3,5-bis (phenylethynyl ) Phenyl] bis [2,5-di- (4-phenylethynyl) phenylcyclopentadienone] (Formula XX Ⅶ ) Synthesis

Example 22 4,4′-bis [(3,5-bis (phenylethynyl) phenyl) glyoxalyl] phenyl ether synthesized using the method of F (8.25 g, 0.01 mol, 2 +/- 1 ppm) Pd), 1,3-bis (4-phenylethynylphenyl) -2-pro synthesized by the method of Example 4B by addition of sodium diethyldithiocarbamate trihydrate by the method described in Example 22 F. Panon (8.62 g, 0.021 mol, containing 2 +/- 1 ppm of Pd), 2-propanol (191 mL) and toluene (63 mL) are added to a 1 L three-neck round bottom reactor. The reactor was a glass stirring chef with a chilled (2 ° C.) condenser, a thermometer with a thermostatic heating mantle, a cryzen adapter, an addition funnel, a nitrogen sparge tube, and a Teflon blade stirrer coupled to a variable speed motor to provide mechanical agitation. I am equipped with a hat. The addition funnel is charged with 1M tetrabutylammonium hydroxide (0.67 mL) in methanol dissolved in 2-propanol (13 mL) under a dry nitrogen atmosphere. Stirring, sparging with nitrogen (1.0 L / min) and heating are started and the slurry stirred at 78 ° C. is completely in solution. In addition, mild reflux is observed at this temperature, the sparging tube is removed and replaced with an overhead inlet for nitrogen. The solution in the addition funnel starts to add to the reflux stirred slurry and completes over 13 minutes during which the yellow solution turns into a dark red amber solution. After an additional 9 minutes, the dark red amber solution becomes a thin granular slurry and after an additional 15 minutes it becomes a thick granular slurry. After an additional 3 minutes, the temperature is now 77 ° C. and additional catalyst solution prepared by dissolving 1M tetrabutylammonium hydroxide (0.34 ml) in methanol under dry nitrogen in 2-propanol (7 ml) is injected into the solution. . After an additional 15 minutes, the heating was stopped and the heating mantle was removed from the reactor and HPLC analysis showed that the 4,4'-bis [(3,5-bis (phenylethynyl) phenyl) glyoxalyl] phenyl ether reactant was completely converted Confirm optimal formation of the desired product and formation of minimal byproducts. At this point, 2-propanol (400 mL) is further added to the reactor to cool the reaction mixture to 50 ° C. within 3 minutes. The product is recovered from the stirred 50 ° C. slurry by vacuum filtration through an intermediate fritted glass funnel. The crystalline product is compressed into a packed cake and then washed with additional 2-propanol on the funnel until the filtrate becomes clear. After air drying on the filter, 32.2 g of the moist product cake was recovered and added to a beaker containing tetrahydrofuran (300 ml, inhibited with butylated hydroxytoluene) and mechanically agitated to provide a solution. The resulting solution is added to an addition funnel and it is added dropwise to a beaker containing magnetically stirred 2-propanol (1.2 L). After the product is recovered from the stirred slurry by vacuum filtration through an intermediate fritted glass funnel, the packed cake is washed with additional 2-propanol on the funnel until the filtrate becomes clear. Dried for 72 hours in a vacuum oven at 30 ° C. to 14.79 g (94.0% isolation yield) of 3,3 ′-(oxy-di-1,4-phenylene) -4,4′-bis [3,5 -Bis (phenylethynyl) phenyl] bis [2,5-di- (4-phenylethynyl) phenylcyclopentadienone] is recovered as a dark red crystalline powder. 95.1 area% of desired 3,3 '-(oxy-di-1,4-phenylene) -4,4'-bis [3,5-bis in a balance comprising four trace byproducts by HPLC analysis It is confirmed that a (phenylethynyl) phenyl] bis [2,5-di- (4-phenylethynyl) phenylcyclopentadienone] monomer is present.

Example 27

3,3 '-(oxy-di-1,4-phenylene) -4,4'-bis [3,5-bis (phenylethynyl) phenyl] -bis [2,5-di- (4-phenyl Differential scanning calorimeter of ethynyl) phenylcyclopentadienone]

3,3 '-(oxy-di-1,4-phenylene) -4,4'-bis [3,5-bis (phenylethynyl) phenyl] bis [2,5- obtained in Example 26 Differential Scanning Calorimetry (DSC) is performed using 3.8 mg of di- (4-phenylethynyl) phenylcyclopentadienone] monomer. DSC 2910 Modular DSC (TA Instruments) is used and a heating rate of 7 ° C./min from 25 ° C. to 500 ° C. under a nitrogen flow stream of 45 cm 2 / min. Exothermic transitions that may contribute to the Diels-Alder reaction of the phenylethynyl and cyclopentadienone groups are observed at maximal at 212.5 ° C. (81.5 joules / g). The onset temperature for this abrupt exothermic transition is 193.5 ° C and the termination temperature is 290.6 ° C. The onset temperature for this exothermic transition is combined with some (approximately enthalpy = 2joules / g) endothermic dissolution transition that is minimal at 193.5 ° C. The second exothermic transition, which may contribute to the reaction of the phenylethynyl group, is maximally observed at 395.9 ° C. (149.1 joules / g). The onset temperature for this exothermic transition is 323.2 ° C and the termination temperature is 493.9 ° C. Secondary scans using the conditions described above showed no glass transition temperature or any other transition. The sample recovered from the DSC analysis is a hard dark amber fused granular solid.

Example 28

Palladium content low 3,3 '-(1,3-phenylene-5-phenylethynyl) -4,4'-bis [(4-phenylethynylphenyl ] Synthesis of Bis [2,5-di- (4-phenylethynyl) phenylcyclopentadienone]

1,3-bis [(4-phenylethynylphenyl) glyoxalyl] -5- synthesized by the method of Example 24 C with the addition of sodium diethyldithiocarbamate trihydrate by the method described in Example 22 F. Phenylethynylbenzene (9.64 g, 0.015 mol, containing 11 +/- 1 ppm of Pd), synthesized by the method of Example 4 B by addition of sodium diethyldithiocarbamate trihydrate by the method described in Example 22 F. 1 l of 1,3-bis (4-phenylethynylphenyl) -2-propanone (containing 12.56 g, 0.0306 mol, 2 +/- 1 ppm of Pd), 2-propanol (177 mL) and toluene (135 mL) It is added to a three-neck round bottom reactor. The reactor was a glass stirring chef with a chilled (2 ° C.) condenser, a thermometer with a thermostatic heating mantle, a cryzen adapter, an addition funnel, a nitrogen sparge tube, and a Teflon blade stirrer coupled to a variable speed motor to provide mechanical agitation. I am equipped with a hat. The addition funnel is charged with 1M tetrabutylammonium hydroxide (0.99 mL) in methanol diluted in 2-propanol (20 mL) under a dry nitrogen atmosphere. Stirring, nitrogen sparging (1.0 L / min) and heating are initiated and at 78 ° C. the product becomes a stirred slurry under gentle reflux. At this temperature the sparging tube is removed and replaced with an overhead inlet for nitrogen. The solution in the addition funnel begins to add to the reflux stirred slurry and completes over 7 minutes during which the yellow slurry turns to a dark amber solution. After an additional 80 minutes, the heating was stopped and the heating mantle was removed from the reactor and HPLC analysis indicated that the 1,3-bis [(4-phenylethynylphenyl) glyoxalyl] -5-phenylethynylbenzene reactant was completely converted to the desired target. Ensure optimal formation of products and formation of minimal byproducts. At this point, 2-propanol (400 mL) is further added to the reactor to cool the reaction mixture to 50 ° C. within 4 minutes. The product is recovered from the stirred 50 ° C. slurry by vacuum filtration through an intermediate fritted glass funnel. The crystalline product is compressed into a packed cake and then washed with additional 2-propanol on the funnel until the filtrate becomes clear. After air drying on the filter, 23.4 g of the moist product cake was recovered and added to a beaker containing tetrahydrofuran (450 mL, inhibited with butylated hydroxytoluene) and mechanically agitated to provide a solution. The resulting solution is added to an addition funnel and it is added dropwise to a beaker containing magnetically stirred 2-propanol (2.4 L). The product is recovered from the stirred slurry by vacuum filtration through an intermediate fritted glass funnel. Dry in a vacuum oven at 30 ° C. for 72 hours to yield 17.95 g (86.0% isolated yield) of 3,3 ′-(1,3-phenylene-5-phenylethynyl) -4,4'-bis [( 4-phenylethynylphenyl] bis [2,5-di- (4-phenylethynyl) phenylcyclopentadienone] is recovered as an intermediate purple crystalline powder, containing two trace byproducts by HPLC analysis 97.1 area% of desired 3,3 '-(1,3-phenylene-5-phenylethynyl) -4,4'-bis [(4-phenylethynylphenyl] bis [2,5- Di- (4-phenylethynyl) phenylcyclopentadienone] monomer is present.

Example 29

3,3 '-(1,3-phenylene-5-phenylethynyl) -4,4'-bis [(4-phenylethynylphenyl] bis [2,5-di- (4-phenylethynyl) Differential Scanning Calorimeter of Phenylcyclopentadienone]

3,3 '-(1,3-phenylene-5-phenylethynyl) -4,4'-bis [(4-phenylethynylphenyl] bis [2,5-di-, obtained in Example 28; Differential Scanning Calorimetry (DSC) is carried out using 2.9 mg of (4-phenylethynyl) phenylcyclopentadienone] monomer 25 with a nitrogen flow stream of 45 cm 2 / min using a DSC 2910 modular DSC (TA Instruments) At a heating rate of 7 ° C./min from 500 ° C. to 500 ° C. An exothermic transition that can contribute to the Diels-Alder reaction of the phenylethynyl and cyclopentadienone groups is observed at 215.5 ° C. (54.6 joules / g) at maximum. The onset temperature for this abrupt exothermic transition is 179.9 ° C. and the termination temperature is 284.5 ° C. A second exothermic transition that can contribute to the reaction of the phenylethynyl group is observed at a maximum at 397.4 ° C. (138.2 joules / g). The onset temperature for the exothermic transition is 308.8 ° C. (138.2 joules / g) and the termination temperature is 492.4 ° C. In the second scan using the conditions described above It was found that there was no glass transition temperature or any other transition The sample recovered from the DSC analysis is a tan granular solid.

Example 30

A. 4,4'- Vis ( Phenoxy ) Benzyl synthesis

Anhydrous 1,2-dichloroethane (100 mL), aluminum chloride (27.20 g, 0.204 mol) followed by diphenyl ether (255.3 g, 1.5 mol) was pre-dried 500 with magnetic stir bar pre-dried under dry nitrogen atmosphere It is added to a ml glass monocyte round bottom Schlenk reactor. The reactor is sealed under dry nitrogen and then placed on a Schlenk line under slightly positive nitrogen pressure. Agitation of the reactor contents is initiated to produce a slurry. Place an ice bath under the reactor 15 minutes before starting the reaction. Oxalyl chloride (12.7 g, 0.10 mol) is added to a pre-dried glass addition funnel under a dry nitrogen atmosphere. The addition funnel is equipped with a Schlenk adapter, sealed under dry nitrogen and placed on a Schlenk line. The reactor and the addition funnel are combined under dynamic nitrogen flow. Oxalyl chloride is added dropwise to the stirred reactor over 45 minutes. 90 minutes after the reaction has passed, the reactor is removed from the Schlenk line and the contents are poured into a 4 l beaker of half ice. Dichloromethane (400 mL) is used to rinse the reaction product remaining in the reactor into an ice beaker. When the ice melts, the contents of the beaker are added to a separatory funnel and removed along the aqueous layer. The organic layer remaining in the separating funnel is washed with deionized water (200 mL) and then the recovered organic layer is dried over anhydrous sodium sulfate and vacuum filtered through an intermediate fritted glass funnel. The filtrate was rotary evaporated to give an oil product (261.4 g) which was added to a beaker containing magnetically stirred hexane (700 mL). The resulting slurry is filtered through an intermediate fritted glass funnel and the white powder on the funnel is washed with sufficient hexane. Drying in a vacuum oven at 80 ° C. yielded 33.24 g (84.3% isolated yield) of 4,4′-bis (phenoxy) benzyl. HPLC analysis confirmed the presence of the desired product at 100 area%.

B. 4,4'- Vis [(3,5- Dibromophenyl ) Acetylphenoxy ] Benzyl synthesis

Anhydrous 1,2-dichloromethane (50 mL) and aluminum chloride (2.93 g, 0.022 mol) are added to a pre-dried 500 mL glass monocytes round bottom Schlenk reactor with magnetic stir bar pre-dried under dry nitrogen atmosphere. The reactor is sealed under dry nitrogen and then placed on a Schlenk line under slightly positive nitrogen pressure. Agitation of the reactor contents is initiated to produce a slurry. Place an ice bath under the reactor 20 minutes before starting the reaction. 4,4'-bis (phenoxy) benzyl (1.97 g, 0.005 mol) obtained in the above A and 3,5-dibromophenylacetyl chloride prepared using the method of Example 22 B (3.12 g, 0.01 mol) is dissolved in anhydrous 1,2-dichloroethane (100 mL) and the resulting solution is added to a pre-dried glass addition funnel under a dry nitrogen atmosphere. The addition funnel is equipped with a Schlenk adapter, sealed under dry nitrogen and placed on the Schlenk line. The reactor and addition funnel are connected under dynamic nitrogen flow. The solution in the addition funnel is added dropwise to the stirred reactor over 145 minutes. After an additional 40 minutes the ice bath is removed from the reactor. After an additional 24 hours, the reactor is removed from the Schlenk line and the contents are poured into a 4 L beaker containing 1.5 L of magnetically stirred deionized water and dichloromethane (1 L) is added. The contents of the beaker are added to a separatory funnel and drained off along the aqueous layer. The organic layer remaining in the separating funnel is washed with deionized water (150 mL) and then vacuum filtered through an intermediate fritted glass funnel. The filtrate was rotary evaporated to give an off white solid (4.98 g) which was added to the beaker with acetonitrile (400 mL), then boiled and cooled to room temperature to give the crystalline product. The crystalline product was recovered by vacuum filtration and dried in a vacuum oven at 80 ° C. to afford 3.23 g (68.3% isolation yield) of 4,4′-bis [(3,5-dibromophenyl) acetylphenoxy] benzyl. To obtain. HPLC analysis confirmed the presence of the desired product at 97.9 area%. The filtrate is rotary evaporated to half the original volume to recover the second crystalline product (1.0 g after drying) and maintained at 4 ° C. HPLC analysis of the second product revealed that the desired product was present at 94.2 area%. EI MS analysis using direct insertion probes confirms the structure of the product: Intact molecular ions are not observed because internal bonds are easily cleaved upon electron ionization. The group of ions concentrated at m / z 473 clearly reflects the isotope pattern of the two bromine atoms for fragment ions of the formula C ₂₁ H ₁₃ O ₃ Br ₂ . This fragment results from cleavage in the central glyoxalyl group and accurately represents half of the molecular structure. Ions concentrated at m / z 197 arise from the center of the molecule. Chemical ionization (CI) is performed to observe intact molecules for molecular ion identification (using isobutane as the CI reagent gas). Samples are introduced using direct exposure probes. The sample applied on the probe wire is heated by ballistic impact from ambient temperature to about 500 ° C. in less than 1 second. In the positive CI mass spectrum, a strong group of quantized molecular ions can be seen around 946 amu and have the isotopic pattern expected for compounds containing four bromine atoms. The group of ions concentrated at m / z 473 reappears in the CI mass spectrum. The structure for 4,4'-bis [(3,5-dibromophenyl) acetylphenoxy] benzyl product is described below:

C. 4,4'- Vis [(3,5- Dibromophenyl ) Glyoxalylphenoxy ] Benzyl synthesis

4,4'-bis [(3,5-dibromophenyl) acetylphenoxy] benzyl (6.0 g, 0.0063 mol) and dimethylsulfoxide (400 mL) obtained in B were stirred with a glass machine with a Teflon paddle. Add to a 1 L glass three-neck round bottom reactor with a rod. The reactor is further equipped with a cryzen adapter, an addition funnel, a chilled (2 ° C.) condenser and a thermometer entering the cleaning facility. Aqueous 48% hydrobromic acid (7.5 g) was added dropwise to the stirred turbid solution at 23 ° C. in the reactor over 1 minute to induce exotherm to 28 ° C. The thermostatic heating mantle is then placed on the reactor and gently heated to 100 ° C. over 48 minutes to yield a pale yellow solution (“heating mildly” periodically stops heating to observe exothermic and equilibrium). To mean). After 2 hours at a reaction temperature of 100 ° C., HPLC analysis confirmed that the reaction was complete. After an additional 35 minutes at a reaction temperature of 100 ° C., the hot product solution is diluted in a 4 L beaker containing 3.0 L of magnetically stirred deionized water. The resulting stirred product slurry is maintained for 16 hours and then vacuum filtered through an intermediate fritted glass funnel. The powder layer packed on the filter is washed with deionized water, which is removed and added to the beaker with acetonitrile (250 mL), then boiled and cooled to room temperature and filtered. The product on the filter was dried from the acetonitrile extract in a vacuum oven at 60 ° C. and then 6.2 g (100% isolation yield) of 4,4′-bis [(3,5-dibromophenyl) glyoxalylphenoxy Benzyl is recovered as a pale yellow powder. HPLC analysis confirmed the presence of 98.5 area% of the desired product in a balance comprising a single trace by-product.

D. 4,4'- Vis [(3,5- Vis ( Phenylethynyl Phenyl) Glyoxalylphenoxy ] Benzyl synthesis

4,4'-bis [(3,5-dibromophenyl) glyoxalylphenoxy] benzyl (4.17 g, 0.0043 mol) obtained in the above C, N, N-dimethylformamide sprayed with dry nitrogen ( 125 g), triethylamine (4.73 g, 0.0467 mol) sparged with dry nitrogen, phenylacetylene (2.11 g, 0.0207 mol), triphenylphosphine (0.114 g, 0.0004 mol) and palladium (II) acetate (0.016 g, 0.00007 mol) is added to a pre-dried 250 mL glass three neck round bottom reactor with magnetic stir bar. The reactor is further equipped with a fan cooled spiral condenser and a thermometer with a thermostatically heated heating mantle. The temperature of 80 ° C. is reached 48 minutes after stirring and heating is started. HPLC analysis after 17 hours at 80 ° C. confirmed that the 4,4′-bis [(3,5-dibromophenyl) glyoxalylphenoxy] benzyl reactant was completely converted. After an additional 3.5 hours at 80 ° C., the product is poured into a 4 L beaker containing 3 L of magnetically stirred deionized water. The resulting stirred product slurry is maintained for 20 hours and then vacuum filtered through an intermediate fritted glass funnel. The product layer packed on the filter is washed with deionized water and then dried in a vacuum oven at 60 ° C. to yield 4.85 g of light golden powder. HPLC analysis confirmed the presence of 96.3 area% of the desired tetraphenylethynyl product in a balance comprising a single byproduct. The product is further purified by dissolving in a boiling solution of magnetically stirred ethanol (350 mL) and acetone (350 mL) and then adding a sufficient amount of deionized water to make it cloudy. Upon cooling, a small amount of material of tarry precipitated from this solution is drained off. The solution is rotary evaporated to yield 3.35 g of product which is further purified by chromatography on neutral silica gel using chloroform as eluent. 3.24 g of 4,4'-bis [(3,5-bis (phenylethynyl) phenyl) glyoxalylphenoxy] benzyl is obtained as crystalline pale yellow powder after rotary evaporation of the eluate obtained from the chromatographic purification. . HPLC analysis revealed that the desired product was present at 98.4 area%.

E. Tetraphenylethynylbis ( Cyclopentadienone ) Monomeric synthesis

4,4'-bis [(3,5-bis (phenylethynyl) phenyl) glyoxalylphenoxy] benzyl (3.22g, 0.00304mol) obtained in the above D, 1,3-diphenylacetone (2.01g) , 0.0096 mol), 2-propanol (100 mL) and toluene (33 mL) are added to a 500 mL three-neck round bottom reactor. The reactor was a glass stirring chef with a chilled (2 ° C.) condenser, a thermometer with a thermostatic heating mantle, a cryzen adapter, an addition funnel, a nitrogen sparge tube, and a Teflon blade stirrer coupled to a variable speed motor to provide mechanical agitation. I am equipped with a hat. The addition funnel is charged with 1M tetrabutylammonium hydroxide (0.39 mL) in methanol diluted in 2-propanol (6 mL) under a dry nitrogen atmosphere. Stirring, sparging with nitrogen (1.0 L / min) and heating are initiated and the slurry stirred at 72 ° C. is completely in solution. Once reaching 79 ° C., mild reflux is observed and the sparging tube is removed and replaced with an overhead inlet for nitrogen. The solution in the addition funnel begins to add to the reflux stirred slurry and is completed over 6 minutes during which the yellow solution turns into a dark red amber solution. After further reacting at 79 to 80 ° C. for 103 minutes, a further catalyst solution prepared by diluting 1M tetrabutylammonium hydroxide (0.195 ml) in methanol in 2-propanol (0.5 ml) under a dry nitrogen atmosphere was injected into the solution. do. After an additional 31 minutes, the dark red solution turns into a thin granular slurry. Two further catalyst solutions (0.1 mL of 1M tetramethylammonium hydroxide in 0.3 mL of 2-propanol and 0.2 mL of 1M tetramethylammonium hydroxide in 0.5 mL of 2-propanol, respectively) after 65 and 41 minutes respectively after the reaction. Inject more. After another 37 minutes, the heating was stopped and the heating mantle was removed from the reactor and HPLC analysis completely converted the 4,4'-bis [(3,5-bis (phenylethynyl) phenyl) glyoxalylphenoxy] benzyl reactant And at the same time confirm the optimal formation of the desired product. Further 2-propanol (150 mL) is added to the reactor and the reaction mixture is cooled to 30 ° C. using a cooling fan outside the reactor. When the stirred slurry reaches 30 ° C., the product is recovered by filtration through an intermediate fritted glass funnel. The product is compressed into a packed cake and then washed with additional 2-propanol on a funnel until the filtrate becomes clear. Drying in a vacuum oven at 30 ° C. for 72 hours recovers 3.80 g of tetraphenylethynylbis (cyclopentadienone) monomer (formula below) as an intermediate purple powder. HPLC analysis confirmed the presence of 72.5 area% of the desired monomer in a balance comprising a single by-product present at 24.3 area% and a minor by-product present at 3.2 area%.

The product is dissolved in a minimum amount of dichloromethane and then further purified by chromatography on neutral silica gel using dichloromethane as eluent. Purity was determined by HPLC analysis of several aliquots of the eluate obtained from the chromatographic purification, followed by HPLC analysis. As a result, 0.74 g of monomer containing 94.3 area% of the desired product and 1.16 g of monomer containing 92.2 area% of the desired product were obtained. It is recovered.

Example 31

Differential Scanning Calorimeter of Tetraphenylethynylbis (cyclopentadienone) Monomer

Differential Scanning Calorimetry (DSC) is performed using 3.9 mg of monomer from 1.16 g of tetraphenylethynylbis (cyclopentadienone) monomer purified chromatographically in Example 30E above. DSC 2910 Modular DSC (TA Instruments) is used and a heating rate of 7 ° C./min from 25 ° C. to 500 ° C. under a nitrogen flow stream of 45 cm 2 / min. Exothermic transitions that may contribute to the Diels-Alder reaction of phenylethynyl and cyclopentadienone groups are observed at 221.2 ° C. (160.6 joules / g) at maximum. The onset temperature for this abrupt exothermic transition is 162.4 ° C and the termination temperature is 346.7 ° C. The onset temperature for this exothermic transition is combined with some endothermic dissolution transition with a minimum at 162.4 ° C. The second exothermic transition, which may contribute to the reaction of the phenylethynyl group, is maximally observed at 445.8 ° C. (6.2 joules / g). The onset temperature for this exothermic transition is 411.2 ° C and the termination temperature is 467.3 ° C. Secondary scans using the conditions described above showed no glass transition temperature or any other transition. The sample recovered from the DSC analysis is a hard dark amber molten solid.

Example 32

Preparation of Porous Matrix from Monomer and Crosslinked Polystyrene Porogens of Formula (IV)

30% 7.2nm crosslinked polystyrene porogen

2.0 g of monomer of Formula IV, crosslinked polystyrene nanoparticles (average peak particle size 7.2 nm as measured by size exclusion chromatography using a laser light scattering detector, prepared from microemulsion polymerization) in a 25 ml round bottom flask and γ Add 4.7 g of butyrolactone (GBL). The resulting mixture is purged with nitrogen for 15 minutes and then heated to 200 ° C. using an oil bath for 2.5 hours under nitrogen. The mixture is then cooled to 145 ° C. and diluted with the same amount of cyclohexanone. The mixture is cooled to room temperature to give a 17.5% polymer mixture in GBL / cyclohexanone.

The mixture is applied to a silicon wafer and cast by spin-coating to form a film 1.0 micron thick. The film is baked for 2 minutes on an MTI hotplate at 150 ° C. and then the applied wafers are transferred to a vacuum oven. The oven temperature is raised to 400 ° C. at 7 ° C./min under nitrogen and held for 120 minutes to decompose and cool the polystyrene porogen. Estimates of average spherical pore size based on small angle X-ray scattering (SAXS) of the film are about 6.5 nm in diameter. The refractive index of the resulting film is 1.506.

Example 33

Preparation of Porous Matrix from Monomer and Crosslinked Polystyrene Porogens of Formula (XII)

30% 7.2nm crosslinked polystyrene porogen

In a 25 ml round bottom flask, 2.0 g of monomer of formula XII, crosslinked polystyrene nanoparticles (average peak particle size 7.2 nm measured by size exclusion chromatography using a laser light scattering detector, prepared from microemulsion polymerization) and γ Add 4.7 g of butyrolactone (GBL). The resulting mixture is purged with nitrogen for 15 minutes and then heated to 200 ° C. using an oil bath for 2.5 hours under nitrogen. The mixture is then cooled to 145 ° C. and diluted with the same amount of cyclohexanone. The mixture is further cooled to room temperature to give a 17.5% polymer mixture in GBL / cyclohexanone.

The mixture is applied to a silicon wafer and cast by spin-coating to form a film 1.0 micron thick. The film is baked for 2 minutes on an MTI hotplate at 150 ° C. and then the applied wafers are transferred to a vacuum oven. The oven temperature is raised to 400 ° C. at 7 ° C./min under nitrogen and held for 120 minutes to decompose and cool the polystyrene porogen. The estimate of average spherical pore size based on small angle X-ray scattering (SAXS) of the film is about 6.9 nm in diameter. The refractive index of the resulting film is 1.514.

Example 34

Preparation of Porous Matrix from Monomers of Formula V and Crosslinked Polystyrene Porogens

30% 7.2nm crosslinked polystyrene porogen

2.0 g of monomer of formula (V), crosslinked polystyrene nanoparticles (average peak particle size 7.2 nm as measured by size exclusion chromatography using a laser light scattering detector, prepared from microemulsion polymerization) in a 25 ml round bottom flask and γ Add 4.7 g of butyrolactone (GBL). The resulting mixture is purged with nitrogen for 15 minutes and then heated to 180 ° C. using an oil bath for 4.0 hours under nitrogen. The mixture is then cooled to 145 ° C. and diluted with the same amount of cyclohexanone. The mixture is further cooled to room temperature to give a 17.5% polymer mixture in GBL / cyclohexanone.

The mixture is applied to a silicon wafer and cast by spin-coating to form a film 1.0 micron thick. The film is baked for 2 minutes on an MTI hotplate at 150 ° C. and then the applied wafers are transferred to a vacuum oven. The oven temperature is raised to 400 ° C. at 7 ° C./min under nitrogen and held for 120 minutes to decompose and cool the polystyrene porogen. The refractive index of the resulting film is 1.539.

Example 35

Preparation of Porous Matrix from Monomer and Crosslinked Polystyrene Porogens of Formula (XXV)

30% 7.2nm crosslinked polystyrene porogen

2.0 g of monomer of Formula XXV, crosslinked polystyrene nanoparticles (average peak particle size 7.2 nm as measured by size exclusion chromatography using a laser light scattering detector, prepared from microemulsion polymerization) in a 25 ml round bottom flask and γ Add 4.7 g of butyrolactone (GBL). The resulting mixture is purged with nitrogen for 15 minutes and then heated to 200 ° C. using an oil bath for 5.0 hours under nitrogen. The mixture is then cooled to 145 ° C. and diluted with the same amount of cyclohexanone. The mixture is further cooled to room temperature to give a 17.5% polymer mixture in GBL / cyclohexanone.

The mixture is applied to a silicon wafer and cast by spin-coating to form a film 1.0 micron thick. The film is baked for 2 minutes on an MTI hotplate at 150 ° C. and then the applied wafers are transferred to a vacuum oven. The oven temperature is raised to 400 ° C. at 7 ° C./min under nitrogen and held for 120 minutes to decompose and cool the polystyrene porogen. The estimate of average spherical pore size based on small angle X-ray scattering (SAXS) of the film is about 6.1 nm in diameter. The refractive index of the resulting film is 1.510.

Example 36

Preparation of Porous Matrix from Monomer and Crosslinked Polystyrene Porogens of Formula (XXVI)

30% 7.2nm crosslinked polystyrene porogen

2.0 g of monomer of Formula XXVI, cross-linked polystyrene nanoparticles (average peak particle size 7.2 nm as measured by size exclusion chromatography using a laser light scattering detector, prepared from microemulsion polymerization) in a 25 ml round bottom flask and mesitylene Add 11.4 g. The resulting mixture is purged with nitrogen for 15 minutes and then heated to 160 ° C. using an oil bath for 12 hours under nitrogen. The mixture is further cooled to room temperature to give a final composition having a solids content of 20%.

The mixture is applied to a silicon wafer and cast by spin-coating to form a film 1.0 micron thick. The film is baked for 2 minutes on an MTI hotplate at 150 ° C. and then the applied wafers are transferred to a vacuum oven. The oven temperature is raised to 400 ° C. at 7 ° C./min under nitrogen and held for 120 minutes to decompose and cool the polystyrene porogen. The refractive index of the resulting film is 1.506.

Example 37

Preparation of Porous Matrix from Monomer and Crosslinked Polystyrene Porogens of Formula (IV)

30% 5.8nm crosslinked polystyrene porogen

To a 25 ml round bottom flask are added 3.0 g of monomer of formula IV and 7.0 g of γ-butyrolactone (GBL). The resulting mixture is purged with nitrogen for 15 minutes and then heated to 200 ° C. under an oil bath for 1.0 hour under nitrogen to prepare an oligomer solution with Mn of 34,000 and Mw of 72,000 g / mol for polystyrene standards. The mixture is then cooled to 145 ° C. and diluted with 5.0 g of cyclohexanone to prepare a solution having a solids content of 20%.

10 g of the solution is then mixed with 0.86 g of crosslinked polystyrene nanoparticles (average peak particle size 5.8 nm, prepared from microemulsification polymerization, measured by size exclusion chromatography using a laser light scattering detector). The mixture is further purged for 15 minutes, then heated to 100 ° C. for 50 minutes and diluted with 3.0 g of cyclohexanone to prepare the final composition.

The mixture is applied to a silicon wafer and cast by spin-coating to form a film 1.0 micron thick. The film is baked for 2 minutes on an MTI hotplate at 150 ° C. and then the applied wafers are transferred to a vacuum oven. The oven temperature is raised to 400 ° C. at 7 ° C./min under nitrogen and maintained for 120 minutes to decompose and cool the polystyrene porogen. The estimate of average spherical pore size based on small angle X-ray scattering (SAXS) of the film is about 5.0 nm in diameter. The refractive index of the resulting film is 1.545.

Example 38

Synthesis of Monomers of Formula V

4,4'-bis [(4-phenylethynylphenyl) glyoxalyl] phenyl ether (1.59 g, 0.0025 mol) obtained in Example 2B and 1,3-bis obtained in B of Example 4 2.26 g (0.0055 mol) of (4-phenylethynylphenyl) -2-propanone are added to a reactor containing 30 ml of anhydrous toluene / 2-propanol (1: 1) mixture. When stirring and heating are initiated and the mixture reaches 80 ° C., tetrabutylammonium hydroxide (1M in methanol, 0.25 ml) is mixed with 8.0 ml of 2-propanol and added dropwise for about 10 to 15 minutes, which immediately gives a deep reddish purple color. Occurs. After maintaining for 1 hour at 80 ° C., HPLC analysis showed that the 4,4′-bis [(4-phenylethynylphenyl) glyoxalyl] phenyl ether reactant was completely converted. At this point the oil bath is removed from the reactor and the reaction mixture is cooled to room temperature. The product is recovered by filtration through an intermediate fritted glass funnel. The crystalline product on the funnel is washed twice with 100 ml of 2-propanol and then dried in a vacuum oven to give 3.1 g (88% isolation yield) of the monomer of formula (V).

Example 40

A tetrafunctional monomer is prepared in which two pyrone functional groups and two acetylene groups are present.

The synthesis sequence is characterized by two stages of continuous Sonogashira binding. Excess trimethylsilylacetylene is reacted with 5-bromo-2-pyron and then the product is desilylated to produce ethynyl-2-pyrone (12) in 81% overall yield. 5-Bromo-2-pyron is reacted with 4,4'-diiododiphenyl ether 13 to give monomer 14 in 11% yield. It is interesting to note that the mono bonds (presumed to yield the following compound 15 from LC and GC-MS) occur very early in the reaction and the bis bonds to compound 14 occur sufficiently slowly so that the bis-bonded acetylene 16 becomes the main product.

Detailed Description: 5-[(trimethylsilyl) ethynyl] -2H-pyran-2-one

N ₂ to a mixture of 5-[(trimethylsilyl) ethynyl] -2H-pyran-2-one (7.9 g, 45 mmol) and trimethylsilylacetylene (8.8 g, 100 mmol) in 1,4-dioxane (600 mL) Dichlorobis (triphenylphosphine) palladium (II) (1.6 g, 0.225 mmol), copper iodide (I) (0.466 g, 0.225 mmol) and triethylamine (4.5 g, 45 mmol) are added with sparging. The mixture is stirred at 20 ° C. for 16 h and then filtered. The solvent is removed under reduced pressure. The residue is dissolved in ether, washed with 1N HCl, saturated NaHCO ₃ and brine and dried (MgSO ₄ ). The organic phase is passed through a silica gel charge and then concentrated under reduced pressure. The residue was purified by silica gel chromatography (5-50% v / v EtOAc / hexanes) to afford the title compound (7.2 g, 84%) as a tan solid. Melting point 82-83 degreeC.

5-ethynyl-2H-pyran-2-one (12)

Tetrabutylammonium fluoride was dissolved in 5-[(trimethylsilyl) ethynyl] -2H-pyran-2-one (0.5 g, 2.6 mmol) and acetic acid (0.6 g, 10 mmol) in THF (50 mL) at 0 ° C. Add dropwise over minutes. The mixture is stirred at 0 ° C. for 1 h and then partitioned between saturated NaHCO ₃ and ether. The organic phase is washed with brine and dried (MgSO ₄ ). The solvent was passed through a silica gel charge followed by evaporation to afford the title compound (0.30 g, 96%) as off-white solid; Melting point 99-100 degreeC.

5,5- [oxybis (4,1-phenylene-2,1-ethyndiyl)] bis-2H-pyran-2-one (14)

N _{2 in} a mixture of 5-ethynyl-2H-pyran-2-one (0.3 g, 2.5 mmol) and 4,4'-dioododiphenyl ether (0.46 g, 1.1 mmol) in 1,4-dioxane Dichlorobis (triphenylphosphine) palladium (II) (89 mg, 0.125 mmol), copper iodide (I) (0.46 mg, 0.25 mmol) and triethylamine (0.25 g, 2.45 mmol) are added with sparging. The mixture is sparged for an additional hour, briefly heated to 50 ° C. and stirred at 20 ° C. for 16 hours. The mixture is filtered and the solvent is evaporated. The residue is taken up in ethyl acetate, washed with 1N HCl, saturated sodium bicarbonate, brine and dried (MgSO ₄ ). The solvent is evaporated and the residue is subjected to reverse phase preparative chromatography using 70:30 CH ₃ CN / H ₂ O as eluent. The product fractions were concentrated to give the title compound (108 mg, 11%) as white crystals; Melting point 204 ~ 205 ℃

It is also isolated from this reaction:

1,1 '-(1,3-butadiin-1,4-diyl) bis-2H-pyran-2-one (16)

As an off-white solid, no melting point was observed at 300 ° C.

The monomer 14 is dispersed in gamma-butyrolactone (15% monomer) and heated to 200 ° C. Samples are taken periodically, analyzed by gel permeation chromatography and visually observed for gel formation. After one hour, Mn is 696 and Mw is 1917. After 1.5 hours a gel is formed, indicating that the resulting polymeric material is not soluble in the solvent.

Claims (25)

At least two dienophile groups and at least two ring structures, wherein the ring structure has two conjugated carbon-carbon double bonds and a leaving group L, and the ring structure is capable of reacting with the dienophile in the presence of an energy source. When the leaving group L is released to form an aromatic ring structure. The monomer of claim 1, wherein 2 to 4 ring structures and 2 to 10 dienophile groups are present. The monomer of claim 1, wherein the monomer is of formula Z-X-Z or Z-X-Z'-X-Z. In the above formula, Z is Is selected from, Z 'is Is selected from, L is -O-, -S-, -N = N-,-(CO)-,-(S0 ₂ )-or -O (CO)-, Each Y independently represents hydrogen, an unsubstituted or inertly substituted aromatic group, an unsubstituted or inertly substituted alkyl group or -WC≡CV, wherein W is an unsubstituted or inertly substituted aromatic group, V is hydrogen, an unsubstituted or inertly substituted aromatic group, or an unsubstituted or inertly substituted alkyl group), X is an unsubstituted or inertly substituted aromatic group or -W-C≡C-W-, wherein W is as defined above, provided that at least two X and Y groups comprise an acetylene group. The chemical formula of claim 1 wherein Monomer. In the above formula, Each Y independently represents hydrogen, an unsubstituted or inertly substituted aromatic group, an unsubstituted or inertly substituted alkyl group or -WC≡CV, wherein W is an unsubstituted or inertly substituted aromatic group, V is hydrogen, an unsubstituted or inertly substituted aromatic group, or an unsubstituted or inertly substituted alkyl group), X is an unsubstituted or inertly substituted aromatic group or -W-C≡C-W-, wherein W is as defined above, provided that at least two X and Y groups comprise an acetylene group. Partially polymerized reaction product of a reaction mixture comprising the monomer according to any one of claims 1 to 4. The partially polymerized reaction product of claim 5, wherein the reaction mixture further comprises one or more additional monomers capable of causing a Diels-Alder reaction with the first monomer. Higher crosslinked polymer prepared by polymerizing a reaction mixture comprising a monomer according to any one of claims 1 to 4. 8. The higher crosslinked polymer of claim 7, wherein the reaction mixture further comprises one or more additional monomers capable of causing a Diels-Alder reaction with the first monomer. A composition comprising an oligomer prepared by partial polymerization of a monomer according to any one of claims 1 to 4. 10. The composition of claim 9 further comprising porogen. The composition of claim 10 wherein the porogen is a polymer having a molecular structure selected from crosslinked nanoparticulate, linear, branched, higher branched, branched, and star shaped structures. The composition of claim 11 wherein the porogen is a crosslinked nanoparticle comprising a styrenic polymer. The composition of claim 11 wherein the porogen is a crosslinked nanoparticle comprising an acrylate or methacrylate based polymer. Containing aromatic groups in the polymer backbone, including functional groups as groups present in the polymer backbone, side chain groups of the polymer backbone, and terminal groups of the polymer chain, wherein the functional groups are each independently a dienophile group, and 2 Selected from the group of ring structures having two conjugated carbon-carbon double bonds and leaving group L, and when the ring structure reacts with the dienophile group in the presence of an energy source, the leaving group L is released to form an aromatic ring structure Branched crosslinkable oligomers or polymers characterized in that the. A reaction mixture comprising the monomer according to any one of claims 1 to 4 is provided, the monomer is partially polymerized by heating to form a composition comprising an oligomer, and the oligomer composition is applied onto a substrate to Forming a film, and curing by further heating the uncured oligomeric film to form a crosslinked aromatic polymer. The method of claim 15, wherein the oligomer is applied by a solvent application method. The method of claim 15, wherein the substrate comprises a semiconductor material and a transistor, and the crosslinked aromatic polymer separates the metal wires. 18. The method of any one of claims 15, 16 and 17, wherein the composition comprising the oligomer further contains a porogen. 19. The method of claim 18, wherein the porogen is removed by heating after the application step. The method of claim 18, wherein the porogen is removed during or after the curing step. A porous film prepared by the method of claim 20. An integrated circuit product made by the method of claim 20. A product made by the method of claim 15. The method of claim 18, wherein the porogen is a crosslinked polymer particle having an average diameter of less than 30 nm. 60. A product made by the method of claim 59, wherein the film has a porosity of 5 to 70 vol% and an average pore size of less than 30 nm.